U.S. patent application number 14/877109 was filed with the patent office on 2016-02-25 for extraction of hydrocarbons from hydrocarbon-containing materials and/or processing of hydrocarbon-containing materials.
This patent application is currently assigned to GREEN SOURCE HOLDINGS LLC. The applicant listed for this patent is GREEN SOURCE HOLDINGS LLC. Invention is credited to Liang-tseng FAN, William Arthur Fitzhugh LEE, Shahram Reza SHAFIE, Julius Michael TOLLAS.
Application Number | 20160053600 14/877109 |
Document ID | / |
Family ID | 41132274 |
Filed Date | 2016-02-25 |
United States Patent
Application |
20160053600 |
Kind Code |
A1 |
FAN; Liang-tseng ; et
al. |
February 25, 2016 |
EXTRACTION OF HYDROCARBONS FROM HYDROCARBON-CONTAINING MATERIALS
AND/OR PROCESSING OF HYDROCARBON-CONTAINING MATERIALS
Abstract
A method of extracting hydrocarbon-containing organic matter
from a hydrocarbon-containing material includes the steps of
providing a first liquid comprising a turpentine liquid; contacting
the hydrocarbon-containing material with the turpentine liquid to
form an extraction mixture; extracting the hydrocarbon material
into the turpentine liquid; and separating the extracted
hydrocarbon material from a residual material not extracted.
Inventors: |
FAN; Liang-tseng; (US)
; SHAFIE; Shahram Reza; (Austin, TX) ; TOLLAS;
Julius Michael; (The Woodlands, TX) ; LEE; William
Arthur Fitzhugh; (Spicewood, TX) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
GREEN SOURCE HOLDINGS LLC |
Austin |
TX |
US |
|
|
Assignee: |
GREEN SOURCE HOLDINGS LLC
Austin
TX
|
Family ID: |
41132274 |
Appl. No.: |
14/877109 |
Filed: |
October 7, 2015 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
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14230281 |
Mar 31, 2014 |
9181468 |
|
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14877109 |
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|
|
13777430 |
Feb 26, 2013 |
8685234 |
|
|
14230281 |
|
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|
12404016 |
Mar 13, 2009 |
8404108 |
|
|
13777430 |
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|
12298993 |
Oct 29, 2008 |
8404107 |
|
|
PCT/US2008/010831 |
Sep 17, 2008 |
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12404016 |
|
|
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|
12174139 |
Jul 16, 2008 |
8272442 |
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12298993 |
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12053126 |
Mar 21, 2008 |
8101812 |
|
|
12174139 |
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60973964 |
Sep 20, 2007 |
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Current U.S.
Class: |
166/265 |
Current CPC
Class: |
C09K 8/54 20130101; Y10T
137/0391 20150401; C10G 21/27 20130101; E21B 43/16 20130101; E21B
43/38 20130101; C09K 8/64 20130101; C09K 8/58 20130101; C10G 1/04
20130101 |
International
Class: |
E21B 43/38 20060101
E21B043/38; E21B 43/16 20060101 E21B043/16; C09K 8/54 20060101
C09K008/54 |
Claims
1. A method of inhibiting the corrosive and toxic effects of a
reactive sulfur species in a sulfur-containing hydrocarbon
containing material from a natural geological formation containing,
comprising: providing a substantially surfactant-free, non-aqueous
turpentine liquid selected from the group consisting of natural
turpentine, synthetic turpentine, mineral turpentine, pine oil,
.alpha.-pinene, .beta.-pinene, .alpha.-terpineol, .beta.-terpineol,
.gamma.-terpineol, terpene resins, .alpha.-terpene, .beta.-terpene,
.gamma.-terpene, geraniol, 3-carene, dipentene
(p-mentha-1,8-diene), nopol, pinane, 2-pinane hydroperoxide, terpin
hydrate, 2-pinanol, dihydromycenol, isoborneol, p-menthan-8-ol,
.alpha.-terpinyl acetate, citronellol, p-menthan-8-yl acetate,
7-hydroxydihydrocitronellal, menthol, anethole, camphene; p-cymene,
anisaldeyde, 3,7-dimethyl-1,6-octadiene, isobornyl acetate,
ocimene, alloocimene, alloocimene alcohols,
2-methoxy-2,6-dimethyl-7,8-epoxyoctane, camphor, citral,
7-methoxydihydro-citronellal, 10-camphorsulphonic acid,
cintronellal, menthone, and mixtures thereof; contacting the
sulfur-containing hydrocarbon-containing material with the
substantially surfactant-free, non-aqueous turpentine liquid such
that at least a portion of the reactive sulfur species from said
sulfur-containing hydrocarbon containing material is extracted into
the substantially surfactant-free, non-aqueous turpentine liquid
from the natural geological formation; and recovering hydrocarbon
containing material from which reactive sulfur species has been
removed such that the corrosive and toxic effects of reactive
sulfur species in the hydrocarbon containing material is
inhibited.
2. The method of claim 1, further comprising separating the
substantially surfactant-free, non-aqueous turpentine liquid
containing the reactive sulfur species from any residual material
that is not soluble in the substantially surfactant-free,
non-aqueous turpentine liquid.
3. The method of claim 1, wherein said sulfur-containing
hydrocarbon containing material is at least one of natural gas,
petroleum gas, crude oil, tar sands, oil shale, asphalt, bitumen,
and coal.
4. The method of claim 1, wherein the reactive sulfur species is at
least one of elemental sulfur, hydrogen sulfide, sulfides,
disulfides, mercaptans, thiophenes, and benzothiophenes.
5. The method of claim 1, wherein said sulfur-containing
hydrocarbon containing material is natural gas or petroleum
gas.
6. The method of claim 5, further comprising bubbling said natural
gas or petroleum gas through said hydrocarbon-extracting liquid to
sweeten the natural gas or petroleum gas.
7. A method of recovering natural gas trapped in a gas reservoir
and avoiding subsidence at the reservoir comprising: injecting into
the reservoir a substantially surfactant-free, non-aqueous
turpentine liquid selected from the group consisting of natural
turpentine, synthetic turpentine, mineral turpentine, pine oil,
.alpha.-pinene, .beta.-pinene, .alpha.-terpineol, .beta.-terpineol,
.gamma.-terpineol, terpene resins, .alpha.-terpene, .beta.-terpene,
.gamma.-terpene, geraniol, 3-carene, dipentene
(p-mentha-1,8-diene), nopol, pinane, 2-pinane hydroperoxide, terpin
hydrate, 2-pinanol, dihydromycenol, isoborneol, p-menthan-8-ol,
.alpha.-terpinyl acetate, citronellol, p-menthan-8-yl acetate,
7-hydroxydihydrocitronellal, menthol, anethole, camphene; p-cymene,
anisaldeyde, 3,7-dimethyl-1,6-octadiene, isobornyl acetate,
ocimene, alloocimene, alloocimene alcohols,
2-methoxy-2,6-dimethyl-7,8-epoxyoctane, camphor, citral,
7-methoxydihydro-citronellal, 10-camphorsulphonic acid,
cintronellal, menthone, and mixtures thereof; maintaining reservoir
pressure using said substantially surfactant-free, non-aqueous
turpentine liquid injection; contacting the natural gas with the
substantially surfactant-free, non-aqueous turpentine liquid such
that at least a portion of the natural gas from the reservoir is
extracted into the substantially surfactant-free, non-aqueous
turpentine liquid to form an extraction mixture; and recovering the
extraction mixture from a production well; and separating said
natural gas from said substantially surfactant-free, non-aqueous
turpentine liquid to form a recycled liquid while maintaining
reservoir pressure.
8. The method of claim 7, further comprising injecting the recycled
liquid into the reservoir.
Description
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] The present application is a Continuation of U.S.
application Ser. No. 14/230,281, filed Mar. 31, 2014, which is a
Continuation of U.S. application Ser. No. 13/777,430, filed Feb.
26, 2013 (now U.S. Pat. No. 8,685,234), which is a Divisional of
U.S. application Ser. No. 12/404,016, filed Mar. 13, 2009 (now U.S.
Pat. No. 8,404,108), which is a continuation-in-part of U.S.
application Ser. No. 12/298,993, filed Oct. 29, 2008 (now U.S. Pat.
No. 8,404,107), which is a 35 U.S.C. .sctn.371 National Phase Entry
Application from PCT/US2008/010831, filed Sep. 17, 2008, and
designating the United States. PCT/US2008/010831 is a
Continuation-in-part of U.S. application Ser. Nos. 12/174,139,
filed Jul. 16, 2008 (now U.S. Pat. No. 8,272,442), and Ser. No.
12/053,126, filed Mar. 21, 2008 (now U.S. Pat. No. 8,101,812), and
claims the benefit of U.S. Provisional Application No. 60/973,964,
filed Sep. 20, 2007, each of which is incorporated by reference in
their entirety.
FIELD OF THE INVENTION
[0002] The present invention relates to the field of extraction of
hydrocarbons from hydrocarbon-containing materials.
BACKGROUND OF THE INVENTION
[0003] The liquefaction, solubilization and/or extraction of fossil
fuels, also called hydrocarbon-containing organic matter, in solid,
semi-solid, highly viscous or viscous form (individually and
jointly referred to as fossil fuels hereafter) have proven to be
extremely challenging and difficult. As used herein, such fossils
fuels include, but are not limited to, hydrocarbon-containing
organic matter within coal, oil shale, tar sands and oil sands
(hereinafter jointly called tar sands), as well as crude oil, heavy
or extra heavy crude oil, natural gas and petroleum gas, crude
bitumen, kerogen, natural asphalt and/or asphaltene. The difficulty
can in part be attributed to the fact that these fossil fuels
include complex organic polymers linked by oxygen and sulfur bonds,
which are often imbedded in the matrices of inorganic compounds. A
need exists to produce additional liquid hydrocarbon feed stock for
the manufacture of liquid and gaseous fuels as well as for the
production of various chemicals, pharmaceuticals and engineered
materials as the demand and consumption for hydrocarbon based
materials increases.
[0004] Various technologies or processes have been developed to
liquefy, solubilize and/or extract the fossil fuels. None of the
prior art liquefaction, solubilization and extraction technologies
or processes, however, has proven to be commercially viable on a
large scale for all types of fossil fuels. This is due to the fact
that all of the prior art technologies and processes for the
liquefaction, solubilization or extraction of hydrocarbons
developed to date are expensive to deploy and operate.
Additionally, the prior art processes and technologies for the
liquefaction, solubilization and/or extraction of hydrocarbons may
be difficult to scale up, operate and/or control because of one or
more of the following reasons: (1) operating at an inordinately
elevated pressure; (2) operating at a very high temperature; (3)
the need for expensive processing vessels and equipment that
require the external supply of hydrogen under extreme conditions;
(4) being subjected to a mixture, or composition, of two or more
reagents, catalysts and/or promoters, which are frequently highly
toxic and are neither renewable nor recyclable; (5) requiring to
supply a special form of energy, e.g., microwave radiation; (6)
long process times for partial liquefaction, solubilization or
extraction; (7) requiring extraordinarily fine particles with a
size of about 200 mesh (0.074 mm), which is profoundly difficult
and costly to manufacture and handle; and (8) being incapable of
recovering and recycling the necessary reagents, catalysts and/or
promoters. Thus, there exists a need to provide additional
techniques and processes for the increased recovery of hydrocarbon
materials.
[0005] In the past, small-scale experiments have shown that
d-limonene solutions can act as solvents for hydrocarbon-containing
materials. However, d-limonene is only partially successful in
solubilizing hydrocarbon-containing materials. Further, because
d-limonene is extracted from citrus rinds, it is available only in
limited quantities and at high cost compared with other
solvents.
[0006] Other solvents used in the past include alkaline solutions
and alcohol-water mixtures. These compositions are only marginally
useful for solubilizing hydrocarbon-containing materials due to the
low solubility of hydrocarbons in aqueous solutions.
[0007] Other prior art methods utilize toluene and/or xylene to
re-liquefy paraffin and thick oil to a less viscous material. Such
methods re-liquefy the paraffins using one or more volatile, very
dangerous, cancer causing chemicals. These products potentially
pollute the ground water and must be handled with extreme caution
as indicated on each chemical's Material Safety Data Sheet. The
paraffin and thick oil revert to their original state once these
products have revolatilized causing deposits in flow lines or
storage tank "dropout".
[0008] "Sour" hydrocarbon-containing materials contain greater than
about 0.5% sulfur by weight. "Sour" gas contains greater than 4 ppm
H.sub.2S and other sulfonated gaseous matter. This sulfur can exist
in the form of free elemental sulfur, hydrogen sulfide gas, and
various other sulfur compounds, including but not limited to,
sulfide, disulfides, mercaptans, thiophenes, benzothiophenes, and
the like. Each crude material or gas may have different amounts or
different types of sulfur compounds, but typically the proportion,
complexity and stability of the sulfur compounds are greatest in
heavier crude oil fractions. Hydrogen sulfide gas is a health
hazard because it is poisonous. Further, hydrogen sulfide can react
with water to form sulfuric acid, which can corrode equipment,
pipelines, storage tanks, and the like. Thus, it is important that
those sulfur-containing hydrocarbon-containing materials that are
reactive be modified to reduce the corrosive effects and to avoid
the health risks associated with untreated sulfur-containing
hydrocarbon-containing materials.
[0009] For primary drilling operations, it would be advantageous to
employ a process that would enhance solubilization and encourage
movement of additional or trapped hydrocarbon-containing organic
matter that could then be recovered allowing existing pressure
gradients to force the hydrocarbon-containing organic matter
through the borehole. In particular, it would be useful to
solubilize heavier hydrocarbons that usually remain in the
reservoir through primary drilling operations.
[0010] For secondary and tertiary or enhanced oil recovery
operations, it would be advantageous to employ a process that would
enhance solubilization of oil to recover hydrocarbon-containing
organic matter in the reservoir in a manner that is cost effective
and that does not damage the reservoir. While effective methods and
compositions exist for tertiary operations, current methods suffer
due to expense of operations in comparison to the value of the
produced hydrocarbon-containing organic matter.
SUMMARY OF INVENTION
[0011] In accordance with one embodiment of the present invention,
a method of extracting hydrocarbon-containing organic matter from a
hydrocarbon-containing material, includes the steps of providing a
first liquid including a turpentine liquid and contacting the
hydrocarbon-containing material with the turpentine liquid such
that an extraction mixture is formed, as well as residual material.
The extraction mixture contains at least a portion of the
hydrocarbon-containing organic matter and the turpentine liquid.
The residual material includes non-soluble material from the
hydrocarbon-containing material. The residual material can also
include a reduced portion of the hydrocarbon-containing organic
matter in the circumstance where all such hydrocarbon-containing
material has not been solubilized by the turpentine liquid and
moved into the extraction mixture. The residual material is then
separated from the extraction mixture. The extraction mixture is
further separated into a first portion and a second portion. The
first portion of the extraction mixture includes a hydrocarbon
product stream that includes at least a portion of the
hydrocarbon-containing organic matter extracted from the
hydrocarbon-containing material. The second portion of the
extraction mixture includes at least a portion of the turpentine
liquid. In one embodiment, at least a portion of the turpentine
liquid is recycled to the hydrocarbon-extracting liquid.
[0012] In another embodiment, substantially all
hydrocarbon-containing organic matter is extracted into the
extraction mixture. In such embodiment, the residual materials are
essentially oil-free and can be further used or disposed without
impact to the environment.
[0013] In another embodiment, the present invention provides a
method for reducing the rate of or inhibiting the corrosion of a
corrodible surface or material. During transportation, drilling,
downhole operations, exploration, hydrocarbon production, storage,
or handling of hydrocarbon-containing material, for example by
pipelines, tankers, casings, fishing tools, or drill bits, the
metal surfaces that contact sulfur-containing compounds in the
hydrocarbon containing materials may corrode. By reducing the
corrosion rate of the corrodible surfaces, significant cost savings
are realized.
BRIEF DESCRIPTION OF THE DRAWINGS
[0014] FIG. 1 is a schematic for one embodiment of an apparatus for
the recovery of hydrocarbons from tar sands.
[0015] FIG. 2 is a schematic for one embodiment of an apparatus for
the recovery of hydrocarbons from oil shale.
[0016] FIG. 3 is a schematic for one embodiment of an apparatus for
the recovery of hydrocarbons from coal.
[0017] FIG. 4 is a schematic for the enhanced recovery of
hydrocarbons from a subsurface reservoir.
[0018] FIG. 5 shows a time course of percentage of bitumen recovery
vs. contact time with various liquids (d-limonene, blend of
turpentine liquids, and water) up to 30 seconds.
[0019] FIG. 6 shows the amount of bitumen recovered over a range of
Liquid to Tar Sands ratios from 1:1 to 6:1 after a 97 second
contact time for the blend of turpentine liquids and
d-limonene.
[0020] FIG. 7 shows the amount of bitumen recovered over a range of
Liquid to Tar Sands ratios from 1:1 to 6:1 after a 5 minute contact
time.
[0021] FIG. 8 shows the amount of bitumen recovered over a range of
Liquid to Tar Sands ratios from 1:1 to 3:1 after a 15 minute
contact time.
DETAILED DESCRIPTION OF THE INVENTION
[0022] In one aspect, the present invention relates to a readily
deployed composition for the extraction, liquefaction and/or
solubilization of fossil fuels from coal, oil shale, tar sands and
the like, as well as from reservoirs.
[0023] According to one embodiment, a method is provided including
the steps of liquefying, solubilizing and/or extracting
hydrocarbon-containing organic matter from a hydrocarbon-containing
material, such as for example, coal, oil shale, tar sands, or a
reservoir containing heavy crude oil, crude oil, natural gas (which
frequently coexists with crude oils and other said fossil fuels),
or a combination thereof. Hydrocarbon-containing organic matter
includes, but is not limited to, heavy crude oil, crude oil,
natural gas, petroleum gas, and the like. Hydrocarbon-containing
organic matter can be solid, semi-solid, liquid, sludge, viscous
liquid, liquid or gaseous form. Other materials that are suitable
hydrocarbon-containing materials for treatment using the method of
this invention include liquids and solids that include
hydrocarbon-containing materials as well as a residual material.
Exemplary hydrocarbon-containing materials can also include oil
tank bottoms, oil pit or pond sludge and slurry mix, discarded
foods, manure, sewage sludge or municipal garbage. Liquefying,
solubilizing and/or extracting the hydrocarbon-containing organic
matter includes the step of providing a hydrocarbon-extracting
liquid, contacting the hydrocarbon-containing material with the
hydrocarbon-extracting liquid so as to extract at least a portion
of said hydrocarbon-containing organic matter from said
hydrocarbon-containing material into said hydrocarbon-extracting
liquid to create an extraction mixture that includes the
hydrocarbon-containing organic matter that has been removed from
the hydrocarbon-containing material and the hydrocarbon-extracting
liquid, and separating the extracted organic matter in the
hydrocarbon-extracting liquid from any residual material not
extracted. The hydrocarbon-extracting liquid can include an amount
of a turpentine liquid, such as for example, terpineol. Turpentine
derived from natural sources generally includes an amount of
terpene. In one embodiment, the turpentine liquid includes
.alpha.-terpineol.
[0024] Another embodiment of the invention comprises contacting the
hydrocarbon-containing material with a turpentine liquid mixture
hereinafter referred to as the blend of turpentine liquids. The
blend of turpentine liquids includes .alpha.-terpineol,
.beta.-terpineol, .beta.-pinene, and p-cymene. In one embodiment,
the multi-component turpentine liquid includes at least about 30%
.alpha.-terpineol, and at least about 15% .beta.-terpineol. In
another embodiment, the blend of turpentine liquids includes about
40-60% .alpha.-terpineol, about 30-40% .beta.-terpineol, about
5-20% .beta.-pinene, and about 0-10% p-cymene. In another
embodiment, the blend of turpentine liquids includes about 50%
.alpha.-terpineol, about 35% .beta.-terpineol, about 10%
.beta.-pinene, and about 5% p-cymene. In an alternative embodiment,
a blend of turpentine liquids includes about 40-60%
.alpha.-terpineol, about 30-40% .alpha.-pinene, about 5-20%
.beta.-pinene, and about 0-10% p-cymene. In another embodiment, a
blend of turpentine liquids includes about 50% .alpha.-terpineol,
about 35% .alpha.-pinene, about 10% .beta.-pinene, and about 5%
p-cymene.
[0025] In certain embodiments, the ratio of turpentine liquid to
hydrocarbon-containing material is in a range of about 1:2 and 6:1
by weight, or in a range of about 1:2 and 4:1 by weight. In another
embodiment the ratio of turpentine liquid to hydrocarbon-containing
material is in a range of about 1:1 and 3:1 by weight. In
embodiments relating to reservoir recovery, the ratio can be
greater than or equal to about 3:1, and in other embodiments
relating to reservoir recovery the ratio can be greater than or
equal to about 4:1. For purposes of extraction from a reservoir,
pore volume is used to determine an estimated measure of the
hydrocarbon-containing material. In other aspects of this
invention, such as in the use of tar sands and coal and oil shale,
volume of the hydrocarbon-containing material can be more directly
estimated.
[0026] In certain embodiments, the minimum organic matter contained
in the hydrocarbon-containing material is greater than or equal to
about 1% by weight, in other embodiments greater than or equal to
about 10% by weight, and in still further embodiments greater than
or equal to about 14% by weight of the hydrocarbon-containing
material.
[0027] Tar sands, coal, oil shale, natural gas, kerogen, bitumen,
asphalt, as used herein, can contain as little as about 1%
naturally occurring hydrocarbon-containing organic matter. The
methods and liquids described are operable to extract up to about
100% of the hydrocarbon-containing organic matter from
hydrocarbon-containing materials containing very low to very high
amounts of hydrocarbons (i.e., material that includes as little as
about 1% by weight hydrocarbon material to material that includes
up to about 100% by weight hydrocarbon material).
[0028] In one embodiment of the invention, a liquefaction,
solubilization or extraction reagent of choice for the
hydrocarbon-containing matter is a natural, synthetic or mineral
turpentine, which can include .alpha.-terpineol, or be
.alpha.-terpineol itself.
[0029] In certain embodiments, the liquefaction, solubilization
and/or extraction of fossil fuels or hydrocarbon-containing organic
matter can be carried out at a temperature within the range of
about 2.degree. C. to about 300.degree. C. In certain embodiments,
the organic matter or material is contacted with a turpentine
liquid at a temperature of less than about 300.degree. C., or less
than about 60.degree. C. In other embodiments, the liquefaction,
solubilization and/or extraction temperatures can be within the
range of about 20.degree. C. to about 200.degree. C. The pressure
under which the liquefaction, solubilization and/or extraction of
fossil fuels is to be carried out may typically be within the range
of about 1.0.times.10.sup.4 Pascals (0.1 atm) to about
5.0.times.10.sup.6 Pascals (50.0 atm). In certain embodiments, the
process can be conducted at a pressure between about
5.0.times.10.sup.4 Pascals (0.5 atm) to about 8.0.times.10.sup.5
Pascals (8.0 atm). In certain other embodiments, the fossil fuels
or hydrocarbon-containing organic matter to be liquefied,
solubilized and/or extracted by immersion in, or contact with, one
or more turpentine liquid can be in the form of particles, pieces,
chunks or blocks of fossil fuels whose sizes are within the range
of about 0.74 mm to about 10 mm into the interior portion of a
liquefaction, solubilization or extraction vessel (hereafter also
referred to as the reactor or contacting vessel interchangeably)
that contains one or more of the said liquefaction, solubilization
and/or extraction reagents. In certain embodiments, the sizes of
the particles, pieces, chunks or blocks of fossil fuels are within
the range of about 0.149 mm (100 mesh) to about 20 mm. In certain
embodiments, the particles, pieces, chunks or blocks of fossil
fuels are agitated by passing the liquefaction, solubilization
and/or extraction reagent or reagents in the form of liquid through
the particles, pieces, chunks or blocks by boiling the reagent or
reagents. In certain embodiments, the duration of liquefaction,
solubilization and/or extraction is from about 1 minute to about 90
minutes. The fossil fuels can be partially or fully liquefied,
solubilized and/or extracted; the degree of liquefaction,
solubilization and/or extraction can be effected by controlling the
operating conditions, such as temperature, pressure, intensity of
agitation and duration of operation, and/or adjusting the type,
relative amount and concentration of the liquefaction,
solubilization or extraction reagent or reagents in the
reactor.
[0030] The basis of one aspect of the present invention is the
unexpected discovery that when about 500 grams of the reagent,
.alpha.-terpineol, were added to about 250 grams of a sample of
coal having a particle diameter of less than about 25 mm from the
Pittsburgh seam in Washington County of Pennsylvania in a tray, the
reagent's color turned pitch black almost immediately, and remained
so after several hours. This indicated that the color change was
not due to the suspension of the coal particles, but rather was
indicative of the extraction of hydrocarbon-containing organic
matter from the coal. Subsequently, this 2:1 mixture of
.alpha.-terpineol and the coal sample was transferred from the tray
to a capped and tightly sealed jar and was maintained under the
ambient conditions of about 20.degree. C. and slightly less than
about 1.01.times.10.sup.5 Pascals (1 atm) for about 25 days. The
conversion, (i.e., the degree of liquefaction), of the coal sample
was determined to be about 71 wt. % after filtering, washing with
ethanol, drying, and weighing. This 71 wt. % conversion corresponds
to nearly all the solubilizable bitumen (organic matter) present in
the coal sample whose proximate analyses are 2.00 wt. % of
as-received moisture, 9.25 wt. % of dry ash, 38.63 wt. % of dry
volatile matter, and 50.12 wt. % of dry fixed carbon. A series of
subsequent experiments with coal, as well as oil shale and tar
sands under various operating conditions, has shown that the family
of reagents that includes natural and/or synthetic turpentines
containing pinenes, and alcohols of pinene, i.e., terpineols, are
inordinately effective in liquefying, solubilizing and/or
extracting kerogen (organic matter), bitumen (organic matter)
and/or asphaltene (organic matter) in the fossil fuels, including
coal, oil shale, tar sands, heavy crude oil and/or crude oil,
without requiring the aid of any catalyst or alkaline metals. These
reagents, except mineral turpentine that is derived from petroleum,
are renewable and "green," i.e., low in toxicity, and relatively
inexpensive, as compared to all other known liquefaction,
solubilization and/or extraction reagents for the fossil fuels,
such as tetraline, xylene, anthracene, and various solutions or
mixtures of these reagents with other compounds. Even mineral
turpentine derived from petroleum, although not renewable, is
relatively low in toxicity, inexpensive, and recyclable. It was
also found that any of the said liquefaction, solubilization and/or
extraction reagents penetrates or diffuses into the particles,
pieces, blocks or chunks of fossil fuels through their pores at
appreciable rates, thus causing these particles, pieces, chunks or
blocks to subsequently release the liquefiable, solubilizable or
extractable fraction in them often almost nearly completely even
under the far milder conditions, e.g., ambient temperature and
pressure, than those required by the recent inventions pertaining
to the liquefaction, solubilization and/or extraction of the fossil
fuels, such as coal, oil shale, tar sands, crude oil and heavy
crude oil.
[0031] An aspect of the present invention provides a method of
liquefying, solubilizing and/or extracting the fossil fuels or
hydrocarbon-containing organic matter from hydrocarbon-containing
material, such as coal, oil shale and tar sands, wherein a portion
of solid or semi-solid fossil fuels is contacted with a turpentine
liquid in an extraction mixture, which can be in an absence of an
alkali metal, catalyst, hydrogen (H.sub.2) and/or carbon monoxide
(CO). While hydrogen and CO can be useful as a mixing agent, one
embodiment of the invention includes the process and the
composition in the absence of hydrogen and CO.
[0032] In certain embodiments, the turpentine liquid is selected
from natural turpentine, synthetic turpentine, mineral turpentine,
pine oil, .alpha.-pinene, .beta.-pinene, .alpha.-terpineol,
.beta.-terpineol, .gamma.-terpineol, polymers thereof, and mixtures
thereof. In certain other embodiments, the turpentine liquid is
selected from geraniol, 3-carene, dipentene (p-mentha-1,8-diene),
nopol, pinane, 2-pinane hydroperoxide, terpin hydrate, 2-pinanol,
dihydromycenol, isoborneol, p-menthan-8-ol, .alpha.-terpinyl
acetate, citronellol, p-menthan-8-yl acetate,
7-hydroxydihydrocitronellal, menthol, and mixtures thereof. In
other embodiments, the turpentine liquid is selected from anethole,
camphene; p-cymene, anisaldeyde, 3,7-dimethyl-1,6-octadiene,
isobornyl acetate, ocimene, alloocimene, alloocimene alcohols,
2-methoxy-2,6-dimethyl-7,8-epoxyoctane, camphor, citral,
7-methoxydihydro-citronellal, 10-camphorsulphonic acid,
cintronellal, menthone, and mixtures thereof.
[0033] The present invention avoids the environmental, economic,
and practical disadvantages that have plagued prior extraction
systems. To date, solvents comprising various surfactants, surface
active agents, alkaline or acidic solutions, salts, volatile
organic compounds, and alcohols have been used with varying degrees
of success. However, each of these known solvent formulations may
have certain drawbacks that one or more embodiments of the current
invention overcome. In one embodiment, the renewable and "green"
extraction liquids of the present invention are naturally derived
and substantially surfactant-free. In another embodiment, the
extraction liquids are surfactant-free. Further, the use of the
extraction liquids of the present invention for extracting
hydrocarbon-containing organic matter from naturally occurring
geological formations avoids the economic and environmental costs
associated with other known liquefaction, solubilization and/or
extraction reagents for fossil fuels.
[0034] In certain embodiments, an aspect of the present invention
provides a method for extracting hydrocarbon-containing materials
using a substantially surfactant-free non-aqueous liquid comprising
a turpentine liquid. Non-aqueous solvents have the advantage of
less leakage into the environment, increased extraction of
hydrocarbons, avoidance of sulfuric acid formation upon contacting
hydrogen sulfide gases and other reactive sulfur compounds trapped
within hydrocarbon containing materials, corrosion inhibition,
viscosity reduction, and capillary effect elimination.
[0035] According to an aspect, solid or semi-solid fossil fuels or
other hydrocarbon-containing materials, such as coal, oil shale,
tar sands and heavy crude oil, or for example oil tank bottoms, oil
pit or pond sludge, discarded foods, manure, sewage sludge or
municipal garbage, may be provided in any size that facilitates
contact with a turpentine liquid. The fossil fuels or
hydrocarbon-containing materials can be provided as particles,
pieces, chunks, or blocks, for example, large fragments or pieces
of coal or oil shale. According to a certain aspect of the
invention, the fossil fuel or hydrocarbon-containing material is
provided as particles. According to a certain aspect of the
invention, the particles of fossil fuel or hydrocarbon-containing
materials have an average particle size of from about 0.01 mm to
about 100 mm. In certain other embodiments, the particles of fossil
fuel have an average particle size from about 4 mm to about 25
mm.
[0036] According to an aspect of the present invention, a second
liquid can be added to the turpentine liquid. According to a
certain aspect of the invention, the second liquid can be selected
from lower aliphatic alcohols, alkanes, aromatics, aliphatic
amines, aromatic amines, carbon bisulfide and mixtures thereof.
Exemplary mixtures include solvents manufactured in petroleum
refining, such as decant oil, light cycle oil and naphtha, or
solvents manufactured in dry distilling coal and fractionating
liquefied coal.
[0037] As used herein, lower aliphatic alcohols refers to primary,
secondary and tertiary monohydric and polyhydric alcohols of
between 2 and 12 carbon atoms. As used herein, alkanes refers to
straight chain and branched chain alkanes of between 5 and 22
carbon atoms. As used herein, aromatics refers to monocyclic,
heterocyclic and polycyclic compounds. As used herein, aliphatic
amines refers to primary, secondary and tertiary amines having
alkyl substituents of between 1 and 15 carbon atoms. In certain
embodiments, benzene, naphthalene, toluene or combinations thereof
are used. In another embodiment, the lower aliphatic alcohols noted
above can be used. In one embodiment the solvent is selected from
ethanol, propanol, isopropanol, butanol, pentane, heptane, hexane,
benzene, toluene, xylene, naphthalene, anthracene, tetraline,
triethylamine, aniline, carbon bisulfide, and mixtures thereof, at
a temperature and pressure operable to maintain the solvent in
liquid form.
[0038] In certain embodiments, the ratio of turpentine liquid to
any other turpentine-miscible solvent contained in said fluid is
greater than or equal to about 1:1, in certain embodiments greater
than or equal to about 9:4. In certain embodiments, the ratio is
greater than or equal to about 3:1. In yet other embodiments, the
ratio is greater than or equal to about 4:1.
[0039] According to an aspect of the present invention, the fossil
fuel and the turpentine liquid are contacted at a temperature of
from about 2.degree. C. to about 300.degree. C. In certain
embodiments, the fossil fuel is contacted by the turpentine liquid
at a temperature of less than about 200.degree. C.
[0040] According to a further aspect of the present invention, the
fossil fuel and the turpentine liquid are contacted at a pressure
of from about 1.0.times.10.sup.4 Pascals (0.1 atm) to about
5.0.times.10.sup.6 Pascals (50 atm). According to an aspect, the
method is executed at a pressure of from about 0.5 atm to about 8
atm.
[0041] According to an aspect of the present invention, the method
further includes providing an extraction vessel within which the
solid or semi-solid fossil fuel is contacted with the turpentine
liquid. According to an aspect, agitation means can be provided
whereby the fossil fuel and the turpentine liquid contained within
the reactor or extractor vessel are mixed and agitated.
[0042] According to an aspect of the present invention, the fossil
fuel and turpentine liquid can be incubated in a holding tank, a
pipeline, or other appropriate vessel so as to prolong their
contact time. According to a further aspect, the degree of
liquefaction, solubilization and/or extraction is controlled by the
length of time the solid or semi-solid fossil fuel is in contact
with the turpentine liquid and/or the temperature of the mixture of
the fossil fuel and turpentine liquid.
[0043] According to an aspect of the present invention, the fossil
fuel is contacted with a heterogeneous liquid including a
turpentine liquid and boiling water as an agitant. The bubbling
action of boiling water causes agitation thereby increasing the
contact surface between the fossil fuel and the turpentine liquid.
Thus, as a result, a higher degree of extraction is observed. After
extraction, the hydrocarbon-containing turpentine liquid may be
separated from water using the difference in liquid densities, e.g.
in a settling tank, decanter, or other separation means known in
the art.
[0044] In certain embodiments, the ratio of turpentine fluid to
water is greater than or equal to about 1:1 by volume, to avoid
slurry formation, which may render separation of the extracted
organic matter in the turpentine liquid-containing fluid
difficult.
[0045] According to an aspect of the present invention, the fossil
fuel is contacted by the turpentine liquid in the presence of an
energy input selected from thermal energy in excess of about
300.degree. C., pressure in excess of 50 atm, microwave energy,
ultrasonic energy, ionizing radiation energy, mechanical
shear-forces, and mixtures thereof.
[0046] According to an aspect of the present invention, a
liquefaction or solubilization catalyst is provided to the mixture
of fossil fuel and turpentine liquid.
[0047] According to an aspect of the present invention, the
reaction or solubilization mixture is supplemented by the addition
of a compound selected from hydrogen, carbon monoxide, water, metal
oxides, metals, and mixtures thereof.
[0048] According to an aspect of the present invention, a
microorganism is included in the reaction or solubilization
mixture. Select chemical bonds, for example, sulfur cross-links and
oxygen cross-links, in the hydrocarbons of fossil fuels and other
hydrocarbon-containing materials are broken by biotreatment with
bacillus-type thermophilic and chemolithotrophic microorganisms
selected from naturally occurring isolates derived from hot sulfur
springs. The breaking of these select chemical bonds facilitates
the solubilization of hydrocarbons in fossil fuels and other
hydrocarbon-containing materials.
[0049] In accordance with one embodiment of the present invention,
a method is provided for extracting hydrocarbon-containing organic
matter from a hydrocarbon-containing material comprising a viscous
liquid, liquid or gaseous fossil fuel material. The method provides
a first liquid that includes a turpentine liquid. The turpentine
liquid is contacted with the hydrocarbon-containing material
in-situ in an underground formation containing said fossil fuel
material, thereby forming an extraction mixture so as to extract
hydrocarbon-containing organic matter into said turpentine liquid
and form an extraction liquid. The extraction liquid is removed
from said formation, wherein the extraction liquid includes the
turpentine liquid containing the extracted hydrocarbon-containing
organic matter. The extracted hydrocarbon-containing organic matter
is separated from a residual material not extracted. The method can
further include separating said extracted hydrocarbon-containing
organic material from the turpentine liquid. The viscous liquid,
liquid or gaseous fossil fuel material can be heavy crude oil,
crude oil, natural gas, or a combination thereof. The underground
formation may be a crude oil reservoir or a natural gas reservoir,
for example.
[0050] The present invention can be deployed readily in-situ to
liquefy and/or solubilize directly the fossil fuels in underground
formations, and extract the resulting liquid products from such
formations.
[0051] An exemplary extraction reagent of the present invention may
be a fluid, e.g. a liquid, which may have a very strong
physicochemical affinity with bituminous organic matter, including
bitumen, kerogen and/or tar, in coal, oil shale and tar sands. When
the extraction reagent of the present invention and bituminous
organic matter comprising mainly hydrocarbons come into direct
contact with each other, the organic matter is extracted into the
extraction reagent of the present invention, thereby liquefying the
organic matter. Upon contact, the hydrocarbons and the extraction
reagent of the present invention rapidly form a homogeneous
solution, i.e., a one-phase liquid.
[0052] It is possible to take advantage of the physicochemical
affinity between the extraction reagent of the present invention
and the bituminous matter for enhancing oil recovery from oil
reservoirs under in-situ conditions. The prior art in-situ recovery
techniques applied to-date in oil reservoirs resort mostly to the
so-called frontal displacement method. This process is strictly
controlled by the characteristics of the multi-phase fluid flow in
a porous medium. This tends to leave a large portion, often
exceeding about 40% of the original oil, unrecovered from the
formation, even for the "good" low viscosity oil reservoirs. The
extraction reagent of the present invention enhances oil recovery
by overcoming the complex behavior of prior multi-phase flow
techniques prevailing under in-situ conditions.
[0053] The present invention provides an improved method for
increasing flowability and extraction of viscous or immobile
hydrocarbon containing materials by contacting a
hydrocarbon-containing material with a turpentine liquid, which
decreases the viscosity of the hydrocarbon-containing material.
Flow is also enhanced by the non-aqueous nature of the turpentine
liquid due to elimination of the capillary effect associated with
aqueous solutions. Contacting can take place in situ or ex
situ.
[0054] The present invention takes advantage of the very strong
physico-chemical affinity of the turpentine liquid.
[0055] One method of the present invention injects an extraction
reagent of the present invention into an oil or natural gas
reservoir through an injection well.
[0056] Oil is extracted into the extraction reagent of the present
invention when the two come into contact in an oil reservoir,
thereby yielding a homogeneous solution, i.e., a one-phase liquid.
The extraction reagent of the present invention does not simply
displace the oil as it travels from the injection well to a
production well in fluid communication with an underground
formation. Rather, extraction of previously trapped oil into the
extraction reagent of the present invention continues until the
extraction reagent is completely exhausted in forming the
homogeneous solution with oil. Thereafter, this homogeneous
solution that includes the extracted hydrocarbons then simply flows
through the pores of the reservoir as a one-phase liquid,
eventually reaching a production well.
[0057] The following examples illustrate three specific embodiments
of in-situ methods for oil recovery of the present invention.
[0058] In a first in-situ embodiment, between about three (3.0) to
seven (7.0) pore volumes of an extraction reagent of the present
invention are injected into an oil reservoir that has previously
been water-flooded to the residual oil saturation while producing
about 51% of the original oil in the reservoir. The subsequent
injection of the extraction reagent can unexpectedly produce about
an additional 41% of the original oil in the reservoir. This
embodiment of the method was experimentally validated, as described
in Example 22 herein below.
[0059] In a second in-situ embodiment, between about two (2.0) to
five (5.0) pore volumes of an extraction reagent of the present
invention are injected into an oil reservoir. At the outset,
injection of the extraction reagent causes only oil to be produced
until about one-third (0.3) to three-quarter (0.75) of pore volume
of the extraction reagent of the present invention is injected;
thereafter, the extraction reagent of the present invention into
which oil has been extracted, is produced. The majority of the oil
present can be recovered upon injecting between about one and a
half (1.5) to three and a half (3.5) total pore volumes of the
reagent. The method unexpectedly recovers about 90% of the original
oil in the reservoir. This embodiment of the method also is
experimentally validated, as described in Example 22 herein
below.
[0060] In a third in-situ embodiment, an extraction reagent of the
present invention is injected to improve the oil recovery from oil
reservoirs containing very viscous oil, e.g., the reservoirs of the
"Orinoco Oil Belt" in Venezuela. The recovery factor for extra
heavy oil with prior art recovery methods is low, typically ranging
from about 10% to about 15% of the original oil in such reservoirs.
The unexpected increase in the recovery efficiency from these
reservoirs with injection of the turpentine liquid extraction
reagent of the present invention can be further enhanced by
adopting horizontal wells for both production and injection wells,
and periodic steam soaking of these wells.
[0061] Ultimate recovery of natural gas from a large gas reservoir
can be increased with the injection of an extraction reagent of the
present invention into a reservoir. The gas production from such a
reservoir often creates dangerously large-scale subsidence on the
surfaces of the gas field, e.g., the "Groeningen" field in the
Netherlands. As such, it is frequently necessary that the reservoir
pressure be maintained by water injection. Water injected into the
reservoir can trap up to about 30% of the gas in-situ at high
pressure due to the two-phase flow of water and gas through the
reservoir with a low permeability. With the injection of an
extraction reagent of the present invention, however, the trapped
gas in the reservoir is extracted into the reagent and flows to the
production wells. By separating the reagent and gas at the surface,
the gas is recovered and the reagent is recycled for reuse.
[0062] The extraction methods of the present invention can be
implemented after one or more of the known methods for facilitating
oil production, e.g., CO.sub.2 or natural gas injection and
surfactant addition, are executed.
[0063] Still other aspects and advantages of the present invention
will become easily apparent by those skilled in the art from this
description, wherein certain embodiments of the invention are shown
and described simply by way of illustration of the best mode
contemplated of carrying out the invention. As will be realized,
the invention is capable of other and different embodiments, and
its several details are capable of modifications in various obvious
respects, without departing from the invention. Accordingly, the
description is to be regarded as illustrative in nature and not as
restrictive.
EXEMPLARY EMBODIMENTS FOR CARRYING OUT THE INVENTION
[0064] Coal
[0065] In certain embodiments, anthracite or bituminous coal can be
ground to sizes ranging from about 0.841 mm (20 mesh) to about
0.149 mm (100 mesh), and subsequently be solubilized and/or
extracted, i.e., liquefied, by immersing in a turpentine liquid
under a pressure within the range of about 1.0.times.10.sup.5
Pascals (1 atm) to about 2.0.times.10.sup.5 Pascals (2.0 atm). In
certain other embodiments, the turpentine liquid can be natural,
synthetic or mineral turpentine that includes up to about 50-70
volume % of .alpha.-terpineol, about 20-40 volume % of
.beta.-terpineol, and about 10 volume % of other components. As
defined herein, the term "other components" can include natural
turpentine, synthetic turpentine, mineral turpentine, pine oil,
.alpha.-pinene, .beta.-pinene, .alpha.-terpineol, .beta.-terpineol,
.gamma.-terpineol, terpene resins, .alpha.-terpene, .beta.-terpene,
.gamma.-terpene, and mixtures thereof. In other embodiments, the
turpentine liquid can include at least one compound selected from
geraniol, 3-carene, dipentene (p-mentha-1,8-diene), nopol, pinane,
2-pinane hydroperoxide, terpin hydrate, 2-pinanol, dihydromycenol,
isoborneol, p-menthan-8-ol, .alpha.-terpinyl acetate, citronellol,
p-menthan-8-yl acetate, 7-hydroxydihydrocitronellal, menthol, and
mixtures thereof. In yet other embodiments, the turpentine liquid
can include at least one compound selected from anethole, camphene;
p-cymene, anisaldeyde, 3,7-dimethyl-1,6-octadiene, isobornyl
acetate, ocimene, alloocimene, alloocimene alcohols,
2-methoxy-2,6-dimethyl-7,8-epoxyoctane, camphor, citral,
7-methoxydihydro-citronellal, 10-camphorsulphonic acid,
cintronellal, menthone, and/or mixtures thereof. In certain
embodiments, the bed of ground anthracite or bituminous coal can be
agitated by passing said turpentine liquid at a temperature in the
range between 80.degree. C. and about 130.degree. C., or possibly
up to the boiling point of said turpentine liquid. In certain other
embodiments, the duration of solubilization and/or extraction,
i.e., liquefaction, can be within about 10 minutes to about 40
minutes. In certain embodiments, the contact time for the
extraction of hydrocarbon-containing organic matter from coal is
less than about 5 minutes.
[0066] In some embodiments, lignite, brown coal, or any other
low-rank coals can be ground to sizes ranging from about 0.419 mm
(40 mesh) to about 0.074 mm (200 mesh), and subsequently be
solubilized and/or extracted, i.e., liquefied, by immersing in a
turpentine liquid under a pressure within the range of about
1.0.times.10.sup.5 Pascals (1 atm) to about 2.0.times.10.sup.5
Pascals (2.0 atm). In certain other embodiments, the turpentine
liquid can be natural, synthetic or mineral turpentine that
includes about 70-90 volume % of .alpha.-terpineol, about 5-25
volume % of .beta.-terpineol, and about 5 volume % of other
components. In other embodiments, the bed of ground lignite, brown
coal, or any other low-rank coals can be agitated by passing said
turpentine liquid at a temperature in the range between about
80.degree. C. and about 130.degree. C., or possibly up to the
boiling point of said turpentine liquid. In certain other
embodiments, the solubilization and/or extraction, i.e.,
liquefaction, can be within about 20 minutes to about 60 minutes.
In certain embodiments, the contact time for the extraction of
hydrocarbon-containing organic matter from coal is less than about
5 minutes.
[0067] Oil Shale
[0068] In certain embodiments, oil shale can be ground to sizes
ranging from about 0.419 mm (40 mesh) to 0.074 mm (200 mesh), and
subsequently be solubilized and/or extracted, i.e., liquefied, by
immersing in a turpentine liquid under a pressure within the range
of about 1.0.times.1.0.sup.5 Pascals (1 atm) to about
2.0.times.10.sup.5 Pascals (2.0 atm). In other embodiments, the
turpentine liquid can be natural, synthetic or mineral turpentine
that includes about 70-90 volume % of .alpha.-terpineol, about 5-25
volume % of .beta.-terpineol, and about 5 volume % of other
components. In certain other embodiments, the bed of ground oil
shale can be agitated by passing said turpentine liquid at a
temperature in the range between about 80.degree. C. and about
130.degree. C., or possibly up to the boiling point of said
turpentine liquid. In other embodiments, the solubilization and/or
extraction, i.e., liquefaction, can be within about 30 minutes to
about 60 minutes. In certain embodiments, the contact time for the
extraction of hydrocarbon-containing organic matter from oil shale
is less than 5 minutes.
[0069] Tar Sands
[0070] In certain embodiments, tar sands can be broken up to sizes
ranging from about 25.4 mm (1 mesh) to 4.76 mm (4 mesh), and
subsequently be solubilized and/or extracted, i.e., liquefied, by
immersing in a turpentine liquid under a pressure within the range
of about 1.0.times.1.0.sup.5 Pascals (1 atm) to about
2.0.times.10.sup.5 Pascals (2.0 atm). In other embodiments, the
turpentine liquid can be natural, synthetic or mineral that
includes containing about 40-60 volume % of .alpha.-terpineol,
about 30-50 volume % of .beta.-terpineol, about 5 volume % of
.alpha. and/or .beta.-pinene and about 5 volume % of other
components. In another embodiment, a bed of ground oil shale can be
agitated by passing said turpentine liquid at a temperature in the
range between about 60.degree. C. and about 90.degree. C., or
possibly up to the boiling point of said turpentine liquid. In
other embodiments, the solubilization and/or extraction, i.e.,
liquefaction, can be within about 10 minutes to about 30 minutes.
In certain embodiments, the contact time for the extraction of
hydrocarbon-containing organic matter from tar sands is less than 5
minutes.
[0071] Crude Oil
[0072] In certain embodiments, light and medium crude oil can be
produced in situ, i.e., removed from an underground reservoir, for
primary, secondary or tertiary recovery, by injecting about one
(1.0) to about five (5.0) pore volumes of a turpentine liquid. In
other embodiments, between about two (2.0) and about four (4.0)
pore volumes of a turpentine liquid can be injected. In certain
embodiments, the turpentine liquid can be natural, synthetic or
mineral turpentine that includes about 40-70 volume % of
.alpha.-terpineol, about 30-40 volume % of .beta.-terpineol, about
10 volume % of .alpha. and/or .beta.-pinene and about 10 volume %
of other components. In certain embodiments, the injection of a
turpentine liquid can be followed by waterflooding with about one
(1.0) to about three (3.0) pore volumes of water.
[0073] In certain embodiments, heavy and extra heavy crude oil can
be produced in situ, i.e., removed from an underground reservoir,
for primary, secondary or tertiary recovery, by injecting about one
(1.0) to about five (5.0) pore volumes of a turpentine liquid. In
other embodiments, between about two (2.0) and about four (4.0)
pore volumes of a turpentine liquid can be injected. In certain
embodiments, the turpentine liquid can be natural, synthetic or
mineral turpentine that includes about 50-70 volume % of
.alpha.-terpineol, about 20-35 volume % of .beta.-terpineol, about
10 volume % of .alpha. and/or .beta.-pinene and about 5 volume % of
other components. In other embodiments, the method can be used in
conjunction with steam injection prior to, during, or after
injection of the hydrocarbon-extracting liquids.
[0074] Referring to FIG. 1, an apparatus for the recovery of
hydrocarbon-containing organic matter from tar sands is provided.
Apparatus 100 includes turpentine liquid supply 102, which can
optionally be coupled to a pump 104, to supply a turpentine liquid
to contacting vessel or extraction vessel 110. In certain
embodiments, the turpentine liquid supply can include means for
heating the turpentine liquid. In certain embodiments, the
contacting vessel can be an inclined rotary filter or trommel. Tar
sands sample 106 is provided to conveyor 108 or like feeding
apparatus for supplying the tar sands to an inlet of contacting
vessel 110. Optionally, conveyor 108 can include a filter screen or
like separating apparatus to prevent large particles from being
introduced into the process. Contacting vessel 110 includes at
least one inlet for turpentine liquid to be introduced and
contacted with the tar sands. Contacting vessel 110 can include a
plurality of trays or fins 114 designed to retain the tar sands in
the contacting vessel for a specified amount of time, and to
increase or control contact between the tar sands particles and the
turpentine liquid. In certain embodiments, the contacting vessel
can be an inclined rotary filter. An extraction mixture that
includes the extracting liquid and hydrocarbon-containing organic
matter extracted from the tar sands is removed from contacting
vessel 110 via outlet 116, which can include filter 118 to prevent
the removal of solids with the extraction mixture that includes the
extracted hydrocarbon-containing organic matter. Pump 120 can be
coupled to outlet 116 to assist with supplying the extraction
mixture to holding tank 122. Line 124 can be coupled to holding
tank 112 for supplying the extraction mixture for further
processing. After extraction of the hydrocarbon-containing organic
matter, inorganic solids and other materials not soluble in the
turpentine liquid can be removed from the contacting vessel via
second conveyor 126. Turpentine liquids operable for the recovery
of hydrocarbons from tar sands utilizing apparatus 100 can include,
but are not limited to, liquids that include .alpha.-terpineol and
.beta.-terpineol.
[0075] Referring now to FIG. 2, apparatus 200 is provided for the
recovery of hydrocarbon-containing organic matter from oil shale
and other sedimentary rock formations that include recoverable
hydrocarbon materials. Oil shale sample 202 is supplied to grinder
or crusher 204 to reduce the size of the oil shale. In one
embodiment, grinder or crusher 204 reduces the oil shale to between
about 0.074 and 0.42 mm in diameter. Crushed oil shale may
optionally be supplied to a filter to ensure uniform and/or
conforming particle size. First conveyor 206 provides particles
from grinder or crusher 204 to contacting vessel 208. Contacting
vessel 208 is coupled to turpentine liquid supply 210, which may
optionally be coupled to a pump, and which supplies a turpentine
liquid to at least one inlet 212 coupled to contacting vessel 208.
In certain embodiments, the turpentine liquid supply can include
means for heating the turpentine liquid. Contacting vessel 208 can
include a plurality of trays or fins 214 designed to retain the tar
sands in the contacting vessel for a specified amount of time, and
to increase or control contact between the tar sands particles and
the turpentine liquid. In certain embodiments, the contacting
vessel can be an inclined rotary filter or trommel. An extraction
mixture stream that includes the turpentine liquid and recovered
hydrocarbon-containing organic matter from the oil shale is
collected via outlet 216 and supplied to holding tank 220. Pump 218
is optionally coupled to outlet 216 to assist with the supply of
the extraction mixture stream to holding tank 220. The extraction
mixture stream can be coupled to line 222 for supplying the
extraction mixture stream to further processing. Second conveyor
224 assists with the removal of inorganic or insoluble materials
from contacting vessel 208. Turpentine liquids operable for the
recovery of hydrocarbons from oil shale utilizing apparatus 200 can
include, but are not limited to, .alpha.-terpineol and
.beta.-terpineol.
[0076] Referring now to FIG. 3, apparatus 300 is provided for the
recovery of hydrocarbon-containing organic matter from coal. Coal
sample 302 is supplied to grinder or crusher 304 to reduce the size
of the coal. In one embodiment, grinder or crusher 304 reduces the
coal to between about 0.01 and 1 mm in diameter, depending upon the
quality of the coal sample. In certain embodiments, the grinder or
crusher 304 can be a wet grinder. Crushed coal may optionally be
supplied to a filter to ensure uniform and/or conforming particle
size. Crushed coal is supplied to first contacting vessel 306.
First contacting vessel 306 is also coupled to a turpentine liquid
supply 308, which may optionally be coupled to pump 310, and which
supplies the turpentine liquid to first contacting vessel 306. In
certain embodiments, the turpentine liquid supply can include means
for heating the turpentine liquid. First contacting vessel 306
includes mixing means 312 designed to agitate and improve or
control contact between the solid coal particles and the turpentine
liquid. An extraction mixture stream that includes the turpentine
liquid and recovered hydrocarbon-containing organic matter from the
oil shale is collected via first contacting vessel outlet 313 and
supplied to second contacting vessel 316. Pump 314 is optionally
coupled to outlet 313 to assist with the supply of the extraction
mixture stream to the second contacting vessel 316. Second
contacting vessel 316 can include a series of trays or fins 318
designed to increase or control separation of the solids and
turpentine liquids. Optionally, the second contacting vessel 316
can be an inclined rotary filter or trommel. The extraction mixture
stream can be collected from second contacting vessel outlet 320,
which may optionally be coupled to pump 322, to assist with supply
of the extraction mixture stream to holding tank 324. Liquid coal
and any turpentine liquid present in holding tank 324 can be
supplied to a liquid coal refinery or other processing step via
line 326. Conveyor 328 can be coupled to second contacting vessel
316 for removal and recovery of the solids as a by-product of the
process. Turpentine liquids operable for the recovery of
hydrocarbons from coal utilizing apparatus 300 can include, but are
not limited to, .alpha.-terpineol and .beta.-terpineol. The
apparatus 300 can also be used to process high and low grade oil
shale.
[0077] Referring now to FIG. 4, process 400 is provided for the
enhanced recovery of hydrocarbon-containing organic matter from a
hydrocarbon-containing subsurface formation. Hydrocarbon-containing
reservoir 404 is shown positioned below the surface 402. Producer
well 406 is already in operation. Injection well 408 is provided
for the injection of a turpentine liquid via line 410. The
turpentine liquid facilitates the liquefaction, solubilization
and/or extraction of hydrocarbon-containing organic matter present
in the reservoir, as well as providing the driving force to push
the hydrocarbon-containing organic matter in the formation toward
the producer well. A hydrocarbon product stream that includes
injected turpentine liquid is collected via line 412. Turpentine
liquids operable for the recovery of hydrocarbons from a
hydrocarbon-containing subsurface formation utilizing apparatus 400
can include, but are not limited to, .alpha.-terpineol and
.beta.-terpineol.
[0078] In certain embodiments, the turpentine liquid for increasing
production from an oil well is provided that includes at least
about 30% by volume of natural turpentine, synthetic turpentine,
mineral turpentine, pine oil, .alpha.-pinene, .beta.-pinene,
.alpha.-terpineol, .beta.-terpineol, .gamma.-terpineol, terpene
resins, .alpha.-terpene, .beta.-terpene, .gamma.-terpene, or
mixtures thereof. In other embodiments, the turpentine liquid
includes at least about 30% by volume geraniol, 3-carene, dipentene
(p-mentha-1,8-diene), nopol, pinane, 2-pinane hydroperoxide, terpin
hydrate, 2-pinanol, dihydromycenol, isoborneol, p-menthan-8-ol,
.alpha.-terpinyl acetate, citronellol, p-menthan-8-yl acetate,
7-hydroxydihydrocitronellal, menthol, or mixtures thereof. In yet
other embodiments, the turpentine liquid includes at least about
30% by volume anethole, camphene; p-cymene, anisaldeyde,
3,7-dimethyl-1,6-octadiene, isobornyl acetate, ocimene,
alloocimene, alloocimene alcohols,
2-methoxy-2,6-dimethyl-7,8-epoxyoctane, camphor, citral,
7-methoxydihydro-citronellal, 10-camphorsulphonic acid,
cintronellal, menthone, or mixtures thereof.
[0079] In certain embodiments, the turpentine liquid includes at
least about 40% by volume .alpha.-terpineol. In other embodiments,
the turpentine liquid includes at least about 25% by volume
.beta.-terpineol. In yet other embodiments, the turpentine liquid
includes at least about 40% by volume .alpha.-terpineol and at
least about 25% by volume .beta.-terpineol. In other embodiments,
the turpentine liquid includes at least about 50%
.alpha.-terpineol, and in certain embodiments also includes
.beta.-terpineol. In certain embodiments, the turpentine liquid
includes at least about 20% by volume of .beta.-terpineol. In
certain embodiments, the turpentine liquid includes between about
50 and 70% by volume of .alpha.-terpineol and between about 10 and
40% by volume of .beta.-terpineol.
[0080] In another aspect, a process for increasing production from
a sub-surface hydrocarbon-containing reservoir undergoing enhanced
recovery operations is provided that includes injecting a
turpentine liquid into the reservoir through an injection well to
stimulate production of the hydrocarbon-containing material. The
turpentine liquid can include at least one compound selected from
natural turpentine, synthetic turpentine, mineral turpentine, pine
oil, .alpha.-pinene, .beta.-pinene, .alpha.-terpineol,
.beta.-terpineol, .gamma.-terpineol, terpene resins,
.alpha.-terpene, .beta.-terpene, .gamma.-terpene, and mixtures
thereof. In other embodiments, the turpentine liquid can include at
least one compound selected from geraniol, 3-carene, dipentene
(p-mentha-1,8-diene), nopol, pinane, 2-pinane hydroperoxide, terpin
hydrate, 2-pinanol, dihydromycenol, isoborneol, p-menthan-8-ol,
.alpha.-terpinyl acetate, citronellol, p-menthan-8-yl acetate,
7-hydroxydihydrocitronellal, menthol, and mixtures thereof. In yet
other embodiments, the turpentine liquid can include at least one
compound selected from anethole, camphene; p-cymene, anisaldeyde,
3,7-dimethyl-1,6-octadiene, isobornyl acetate, ocimene,
alloocimene, alloocimene alcohols,
2-methoxy-2,6-dimethyl-7,8-epoxyoctane, camphor, citral,
7-methoxydihydro-citronellal, 10-camphorsulphonic acid,
cintronellal, menthone, and mixtures thereof. A
hydrocarbon-containing organic matter production stream that
includes the turpentine liquid and recovered hydrocarbons is
recovered from a producer well associated with the
hydrocarbon-containing reservoir. The hydrocarbon-containing
organic matter production stream can be separated into a recovered
hydrocarbons stream and a turpentine liquid for recycle. In certain
embodiments, the method can further include the step of injecting
the turpentine liquid recycle stream into the injection well.
[0081] In another aspect, a method for recovering
hydrocarbon-containing organic matter from hydrocarbon-containing
coal rich sub-surface formation is provided. The method includes
the steps of extracting the hydrocarbon-containing organic matter
by a process consisting essentially of the steps of obtaining coal
sample that includes a recoverable hydrocarbon-containing organic
matter and grinding the coal to produce crushed coal. The crushed
coal is filtered and fed to a contacting vessel that includes at
least one inlet for supplying a hydrocarbon extracting liquid to
the contacting vessel. The crushed coal is contacted with a
substantially surfactant-free non-aqueous hydrocarbon-extracting
liquid consisting essentially of a turpentine liquid selected from
the group consisting of natural turpentine, synthetic turpentine,
mineral turpentine, pine oil, .alpha.-pinene, .beta.-pinene,
.alpha.-terpineol, .beta.-terpineol, .gamma.-terpineol, terpene
resins, .alpha.-terpene, .beta.-terpene, .gamma.-terpene, geraniol,
3-carene, dipentene (p-mentha-1,8-diene), nopol, pinane, 2-pinane
hydroperoxide, terpin hydrate, 2-pinanol, dihydromycenol,
isoborneol, p-menthan-8-ol, .alpha.-terpinyl acetate, citronellol,
p-menthan-8-yl acetate, 7-hydroxydihydrocitronellal, menthol,
anethole, camphene; p-cymene, anisaldeyde,
3,7-dimethyl-1,6-octadiene, isobornyl acetate, ocimene,
alloocimene, alloocimene alcohols,
2-methoxy-2,6-dimethyl-7,8-epoxyoctane, camphor, citral,
7-methoxydihydro-citronellal, 10-camphorsulphonic acid,
cintronellal, menthone, and mixtures thereof, such that an
extraction mixture is formed and a residual material is formed. The
extraction mixture includes at least a portion of the
hydrocarbon-containing organic matter in the turpentine liquid, and
the residual material includes at least a portion of non-soluble
material from the coal that is not soluble in the turpentine
liquids. The residual material is separated from the extraction
mixture, and the hydrocarbon-containing material organic matter is
separated from the turpentine liquid to produce a hydrocarbon
product stream and a turpentine liquid stream, wherein the
hydrocarbon product stream includes at least a portion of the
hydrocarbon-containing organic matter from the coal. At least a
portion of the turpentine liquid stream is recycled to the
contacting step.
[0082] In another aspect, a method for increasing production from a
hydrocarbon-containing sub-surface hydrocarbon formation undergoing
enhanced recovery operations is provided. The method includes the
steps of injecting a turpentine liquid into the formation through
an injection well. In certain embodiments, the turpentine liquid
includes at least about 40% by volume .alpha.-terpineol and at
least about 10% by volume .beta.-terpineol. The turpentine liquid
solubilizes, extracts and/or displaces the hydrocarbon-containing
materials from the formation, which are subsequently recovered from
the formation with the turpentine liquid through a producer well.
In certain embodiments, the method further includes separating the
hydrocarbons from the turpentine liquid. In yet other embodiments,
the method further includes recycling the turpentine liquid to the
injection well. In certain embodiments, .alpha.-terpineol is
present in an amount between about 40 and 70% by volume. In certain
other embodiments, .alpha.-terpineol is present in an amount of at
least about 70% by volume. In yet other embodiments,
.beta.-terpineol is present in an amount between about 10 and 40%
by volume. In other embodiments, the turpentine liquid further
includes up to about 10% by volume .gamma.-terpineol. In other
embodiments, the turpentine liquid can include up to about 25% by
volume of an organic solvent selected from methanol, ethanol,
propanol, toluene and xylenes. The method is useful for the
recovery of hydrocarbon-containing organic matter during primary,
secondary and tertiary recovery operations, including after
secondary recovery operations that include waterflooding.
[0083] In another aspect, a turpentine liquid for the recovery of
hydrocarbon-containing organic matter from tar sands is provided.
In one embodiment, the turpentine liquid includes at least about
30% by volume .alpha.-terpineol and at least about 25% by volume
.beta.-terpineol. In another embodiment, the turpentine liquid
includes between about 30 and 70% by volume .alpha.-terpineol,
between about 25 and 55% by volume .beta.-terpineol, up to about
10% by volume .alpha.-terpene, and up to about 10% by volume
.beta.-terpene.
[0084] In another aspect, a turpentine liquid for recovering
hydrocarbon-containing organic matter from high grade coal sources,
such as for example, anthracite or bituminous coal, is provided. In
one embodiment, the turpentine liquid includes at least about 45%
by volume .alpha.-terpineol and at least about 15% by volume
.beta.-terpineol. In another embodiment, the turpentine liquid
includes between about 45 and 80% by volume .alpha.-terpineol,
between about 15 and 45% by volume .beta.-terpineol, up to about
10% by volume .alpha.-terpene, and up to about 10% by volume
.beta.-terpene.
[0085] In another aspect, a turpentine liquid for recovering
hydrocarbon-containing organic matter from low grade coal sources
is provided. In one embodiment, the turpentine liquid includes at
least about 60% by volume .alpha.-terpineol and up to about 30% by
volume .beta.-terpineol. In another embodiment, the turpentine
liquid includes between about 60 and 95% by volume
.alpha.-terpineol, up to about 30% by volume .beta.-terpineol, up
to about 5% by volume .alpha.-terpene, and up to about 5% by volume
.beta.-terpene.
[0086] In another aspect, a turpentine liquid for recovering
hydrocarbon-containing organic matter from oil shale is provided.
As used herein, oil shale generally refers to any sedimentary rock
that contains bituminous materials. In one embodiment, the
turpentine liquid includes at least about 60% by volume
.alpha.-terpineol and up to about 30% by volume .beta.-terpineol.
In another embodiment, the turpentine liquid includes between about
60 and 95% by volume .alpha.-terpineol, up to about 30% by volume
.beta.-terpineol, up to about 5% by volume .alpha.-terpene, and up
to about 5% by volume .beta.-terpene.
[0087] In another aspect, a turpentine liquid is provided for
recovering hydrocarbon-containing organic matter from light and
medium crude oil. In one embodiment, the turpentine liquid includes
at least between about 40 and 70% by volume .alpha.-terpineol and
at least between about 30 and 40% by volume .beta.-terpineol. In
yet another embodiment, the turpentine liquid includes between
about 40 and 70% by volume .alpha.-terpineol, between about 30 and
40% by volume .beta.-terpineol, up to about 10% by volume
.alpha.-terpene, and up to about 10% by volume .beta.-terpene.
[0088] In another aspect, a turpentine liquid is provided for
recovering hydrocarbon-containing organic matter from heavy and
extra heavy crude oil. In one embodiment, the turpentine liquid
includes at least between about 50 and 70% by volume
.alpha.-terpineol and at least between about 30 and 40% by volume
.beta.-terpineol. In another embodiment, the turpentine liquid
includes between about 50 and 70% by volume .alpha.-terpineol,
between about 30 and 40% by volume .beta.-terpineol, up to about
10% by volume .alpha.-terpene, and up to about 10% by volume
.beta.-terpene.
[0089] In another aspect, a method for recovering
hydrocarbon-containing organic matter from tar sands is provided.
The method includes obtaining a tar sand sample, such as for
example, by mining a formation rich in tar sands to provide a tar
sands sample, wherein the tar sands sample includes a recoverable
hydrocarbon-containing organic matter and residual inorganic or
insoluble material. The tar sands sample is supplied to a
contacting vessel, wherein the contacting vessel includes at least
one inlet for supplying a hydrocarbon-extracting liquid that
consists essentially of a turpentine liquid for recovery of
hydrocarbons from the tar sands. The tar sands sample is contacted
with a hydrocarbon-extracting liquid and agitated to extract the
hydrocarbon-containing organic matter from the tar sands to produce
a residual material and an extraction mixture. The extraction
mixture includes the hydrocarbon-extracting liquid and recovered
hydrocarbon-containing organic matter, and the residual material
which includes at least a portion of the non soluble material. The
extraction mixture is separated from the residual material, and is
further separated into a hydrocarbon product stream and a
hydrocarbon-extracting liquid stream, wherein the
hydrocarbon-extracting liquid stream includes at least a portion of
the hydrocarbon-containing organic matter extracted from the tar
sands. In certain embodiments, the method further includes the step
of recycling the turpentine liquid stream to the contracting
vessel. In other embodiments, the extraction mixture can be
separated by distillation to produce the hydrocarbon product stream
and the turpentine liquid recycle stream.
[0090] In certain embodiments, the turpentine liquid can include
.alpha.-terpineol. In other embodiments, the turpentine liquid can
include at least about 40% by volume .alpha.-terpineol and between
about 10 and 40% by volume .beta.-terpineol. In certain
embodiments, between about 0.5 and 4 equivalents of the turpentine
liquid is used to contact the tar sands and recover hydrocarbons.
In certain embodiments, between about 0.5 and 2.0 equivalents of
the turpentine liquid is used to contact the tar sands and recover
hydrocarbons.
[0091] In another aspect, a method for recovering
hydrocarbon-containing organic matter from a hydrocarbon rich oil
shale is provided. The method includes mining a rock formation that
includes hydrocarbon-containing organic matter to produce a
hydrocarbon containing oil shale that includes a recoverable
hydrocarbon material and inorganic or insoluble material. The oil
shale is ground to produce comminuted hydrocarbon-containing oil
shale. The comminuted hydrocarbon-containing oil shale is then
filtered with a filter screen to prevent or control the excessively
large particles from being supplied to the extraction process. The
comminuted hydrocarbon-containing oil shale is fed to a contacting
vessel, wherein the contacting vessel includes at least one inlet
for supplying a hydrocarbon-extracting liquid consisting
essentially of a turpentine liquid for recovery of hydrocarbons
from the crushed hydrocarbon-containing oil shale. The comminuted
hydrocarbon-containing oil shale is contacted with the
hydrocarbon-extracting liquid such that an extraction mixture is
formed and a residual material is formed, wherein the extraction
mixture includes at least a portion of the hydrocarbon-containing
organic matter in the hydrocarbon-extracting solvent and the
residual material includes at least a portion of the non-soluble
material from the oil shale. The extraction mixture is separated
from the residual material. The hydrocarbon-containing organic
matter from the hydrocarbon-extracting liquid in the extraction
mixture are separated from the turpentine liquid to produce a
hydrocarbon product stream that includes at least a portion of the
hydrocarbon-containing organic matter and a hydrocarbon-extracting
liquid stream. In certain embodiments, the turpentine liquid stream
is recycled to the contacting vessel. In other embodiments, the
comminuted hydrocarbon-containing oil shale has a mean particle
size of less than about 0.4 mm in diameter. In other embodiments of
the method for the recovery of hydrocarbon-containing organic
matter from oil shale, the turpentine liquid includes at least one
compound selected from natural turpentine, synthetic turpentine,
mineral turpentine, pine oil, .alpha.-pinene, .beta.-pinene,
.alpha.-terpineol, .beta.-terpineol, .gamma.-terpineol, terpene
resins, .alpha.-terpene, .beta.-terpene, .gamma.-terpene, or
mixtures thereof. In other embodiments, the turpentine liquid
includes at least one compound selected from geraniol, 3-carene,
dipentene (p-mentha-1,8-diene), nopol, pinane, 2-pinane
hydroperoxide, terpin hydrate, 2-pinanol, dihydromycenol,
isoborneol, p-menthan-8-ol, .alpha.-terpinyl acetate, citronellol,
p-menthan-8-yl acetate, 7-hydroxydihydrocitronellal, menthol, and
mixtures thereof. In other embodiments, the turpentine liquid
includes at least one compound selected from anethole, camphene;
p-cymene, anisaldeyde, 3,7-dimethyl-1,6-octadiene, isobornyl
acetate, ocimene, alloocimene, alloocimene alcohols,
2-methoxy-2,6-dimethyl-7,8-epoxyoctane, camphor, citral,
7-methoxydihydro-citronellal, 10-camphorsulphonic acid,
cintronellal, menthone, and mixtures thereof. In certain
embodiments, the turpentine liquid can include .alpha.-terpineol.
In other embodiments, the turpentine liquid can include at least
about 40% by volume .alpha.-terpineol and between about 10 and 40%
by volume .beta.-terpineol. In certain embodiments, between 0.5 and
4 equivalents of the turpentine liquid is used to contact the oil
shale and recover hydrocarbon-containing organic matter. In certain
embodiments, between 0.5 and 2.0 equivalents of the turpentine
liquid is used to contact the oil shale and recover
hydrocarbons.
[0092] In another aspect, a method for recovering
hydrocarbon-containing organic matter from a coal rich sub-surface
formation is provided. The method includes obtaining a coal, such
as for example, by mining the sub-surface formation to produce
coal, wherein the coal includes a recoverable
hydrocarbon-containing organic matter and inorganic or insoluble
material. The coal is ground to produce crushed coal and filtered
to provide a sample of uniform or desired size. The crushed coal is
fed to a contacting vessel, wherein the contacting vessel includes
at least one inlet for supplying a hydrocarbon-extracting liquid
consisting essentially of a turpentine liquid for recovery of
hydrocarbons from crushed coal, and contacted with the
hydrocarbon-extracting liquid such that an extraction mixture is
formed and a residual material is formed, wherein the extraction
mixture includes at least a portion of the hydrocarbon-containing
organic matter in the hydrocarbon-extracting liquid. The residual
mixture includes at least a portion of non-soluble material from
the coal. The residual matter is separated from the extraction
mixture. Hydrocarbon containing organic matter is separated from
the hydrocarbon-containing liquid to produce a hydrocarbon product
stream that includes at least a portion of the hydrocarbon
containing organic matter from the coal and a
hydrocarbon-extracting liquid stream. In certain embodiments, the
method further includes recycling the hydrocarbon-extracting liquid
stream to the contacting vessel. In yet other embodiments, the
liquid coal product stream is supplied to a liquid coal refinery.
In certain embodiments, the coal sample includes a low grade coal
having a mean particle size of less than about 0.4 mm. In certain
embodiments, the coal sample includes a high grade coal having a
mean particle size of less than about 1 mm.
[0093] In yet other embodiments of the method for recovering
hydrocarbon-containing organic matter from coal, the turpentine
liquid includes at least one compound selected from natural
turpentine, synthetic turpentine, mineral turpentine, pine oil,
.alpha.-pinene, .beta.-pinene, .alpha.-terpineol, .beta.-terpineol,
.gamma.-terpineol, terpene resins, .alpha.-terpene, .beta.-terpene,
.gamma.-terpene, or mixtures thereof. In other embodiments, the
turpentine liquid includes at least one compound selected from
geraniol, 3-carene, dipentene (p-mentha-1,8-diene), nopol, pinane,
2-pinane hydroperoxide, terpin hydrate, 2-pinanol, dihydromycenol,
isoborneol, p-menthan-8-ol, .alpha.-terpinyl acetate, citronellol,
p-menthan-8-yl acetate, 7-hydroxydihydrocitronellal, menthol, and
mixtures thereof. In other embodiments, the turpentine liquid
includes at least one compound selected from anethole, camphene;
p-cymene, anisaldeyde, 3,7-dimethyl-1,6-octadiene, isobornyl
acetate, ocimene, alloocimene, alloocimene alcohols,
2-methoxy-2,6-dimethyl-7,8-epoxyoctane, camphor, citral,
7-methoxydihydro-citronellal, 10-camphorsulphonic acid,
cintronellal, menthone, and mixtures thereof. In certain
embodiments, the turpentine liquid includes at least 60 about by
volume .alpha.-terpineol. In certain embodiments, the turpentine
liquid includes at least about 45% by volume .alpha.-terpineol and
at least about 15% by volume .beta.-terpineol. In certain other
embodiments, the turpentine liquid includes at least about 60% by
volume .alpha.-terpineol and up to about 30% by volume
.beta.-terpineol. In certain embodiments, between about 0.5 and 4
equivalents of the turpentine liquid is used to contact the coal
and recover hydrocarbon-containing organic matter. In certain
embodiments, between 0.5 and 2.0 equivalents of the turpentine
liquid is used to contact the oil shale and recover
hydrocarbon-containing organic matter.
[0094] In another aspect, a method for increasing recovery of
hydrocarbon-containing organic matter from a production well is
provided, wherein the production well is coupled to a
hydrocarbon-containing sub-surface formation that includes
hydrocarbon-containing material. The method includes the steps of
extracting the hydrocarbon-containing organic matter by a process
that includes the steps of providing an injection well that is in
fluid communication with the sub-surface formation. A substantially
surfactant-free first liquid is provided that includes a
non-aqueous hydrocarbon-extracting liquid consisting essentially of
a turpentine liquid that includes terpineol. The
hydrocarbon-extracting liquid is injected through the injection
well and into the formation, wherein the hydrocarbon-extracting
liquid and the hydrocarbon-containing organic matter from the
hydrocarbon containing sub-surface formation form an extraction
mixture that includes at least a portion of the extraction mixture
hydrocarbon-containing organic matter in at least a portion of the
turpentine liquid. The extraction mixture is recovered from the
formation through the production well, and the extraction mixture
to produce a hydrocarbon product stream and a turpentine liquid
stream.
[0095] In another aspect, a system for recovering
hydrocarbon-containing organic material from tar sands is provided.
The tar sands recovery system includes a tank for supplying a
turpentine liquid and a contacting vessel, wherein the contacting
vessel includes at least one inlet for introducing the turpentine
liquid and at least one outlet for recovering an extraction mixture
from the contacting vessel. The system also includes a first
conveyor for supplying tar sands to the contacting vessel. A
holding tank that includes a line connecting the holding tank to
the contacting vessel is provided, wherein the line connecting the
contacting vessel and the holding tank includes a filter to prevent
the passage of solids to the holding tank. The system also includes
a second conveyor for the recovery and transport of the solids.
[0096] In one embodiment, the contacting vessel is a rotary
inclined filter that includes a series of fins or trays for
separating and or controlling the tar sands. In another embodiment,
the fins or trays are provided to increase or control the contact
time between the tar sands and the turpentine liquid. In certain
embodiments, the turpentine liquid can include .alpha.-terpineol.
In other embodiments, the turpentine liquid can include between
about 30% and about 70% by volume .alpha.-terpineol and between
about 25% and about 55% by volume .beta.-terpineol.
[0097] In another aspect, a system for recovering
hydrocarbon-containing organic matter from oil shale is provided.
The system includes a tank for supplying a turpentine liquid and a
grinder for comminuting the oil shale to a reduced particle size. A
contacting vessel is provided that includes at least one inlet for
introducing the turpentine liquid, at least one inlet for receiving
crushed oil shale, at least one outlet for recovering solids from
the contacting vessel and at least one outlet for recovering an
extraction mixture from the contacting vessel. A first conveyor is
provided for supplying crushed oil shale to a contacting vessel.
The system further includes a holding tank, wherein the holding
tank includes a line connecting the holding tank to the contacting
vessel, wherein the line includes a filter to prevent the passage
of solids to the holding tank; a second conveyor for recovering
solids. In certain embodiments, the system further includes a line
for supplying a reaction mixture including recovered hydrocarbons
and the turpentine liquid to a refinery for further separation
and/or processing. In certain embodiments, the turpentine liquid
can include .alpha.-terpineol. In certain embodiments, the
turpentine liquid can include between about 60% and about 95% by
volume .alpha.-terpineol and up to about 30% by volume
.beta.-terpineol. In other embodiments, the turpentine liquid can
include between about 70% and about 90% by volume .alpha.-terpineol
and between about 5% and about 25% by volume .beta.-terpineol.
[0098] In another aspect, a system for recovering
hydrocarbon-containing organic matter from coal is provided. The
system includes a tank for supplying a turpentine liquid and a
grinder for comminuting coal to produced particulate matter of a
reduced size. Optionally, the system can include a filter to
restrict the introduction of large particles. A contacting vessel
is provided that includes at least one inlet for introducing the
turpentine liquid and at least one outlet for recovering solids and
liquids from the contacting vessel. The contacting vessel includes
also stirring means for thoroughly mixing the turpentine liquid and
the comminuted coal. A separator is provided for separating the
solids and liquids, wherein the separator includes an inlet, an
outlet and a line connecting the inlet of the separator to the
outlet of the contacting vessel. The system also includes a holding
tank, wherein the holding tank includes a line that connects the
holding tank to the separator, wherein the line can include a
filter to prevent the passage of solids to the holding tank.
[0099] In certain embodiments, the system further includes a filter
for selectively preventing particles having a mean diameter greater
than about 1 mm from being introduced to the contacting vessel. In
certain other embodiments, the system further includes a line for
supplying a liquid coal product to a refinery for further
processing. In certain embodiments, the system further includes a
first conveyor for supplying crushed coal to the contacting vessel.
In other embodiments, the system further includes a second conveyor
for removing solids from the separator. In certain embodiments, the
turpentine liquid can include .alpha.-terpineol. In embodiments
directed to the recovery of hydrocarbons from high grade coal, the
turpentine liquid can include between about 45% and about 80% by
volume .alpha.-terpineol and between about 15% and about 45% by
volume .beta.-terpineol. In embodiments directed to the recovery of
hydrocarbons from low grade coal, the turpentine liquid can include
between about 60% and about 95% by volume .alpha.-terpineol and
between about 0% and about 30% by volume .beta.-terpineol.
[0100] In certain embodiments, the hydrocarbon-extracting liquid
can be separated from hydrocarbon-containing organic matter at,
adjacent to, or in close proximity to the site of extraction of the
hydrocarbon-containing material, i.e. coal, oil shale, tar sands,
crude oil, heavy crude oil, natural gas and petroleum gas, crude
bitumen, kerogen, natural asphalt and/or asphaltene.
[0101] In further embodiments, the hydrocarbon-extracting liquid
can be partially separated from hydrocarbon-containing organic
matter at, adjacent to, or in close proximity to the site of
extraction. In such embodiments, a portion of the
hydrocarbon-extracting liquid is allowed to remain in the
hydrocarbon-containing organic matter, thereby reducing viscosity
and preventing corrosion during storage and transport.
[0102] In other embodiments, separation of the
hydrocarbon-extracting liquid from hydrocarbon-containing organic
matter occurs at a downstream facility which may be distant from
the site of extraction, e.g. at a refinery.
[0103] In another aspect, partial or full separation of
hydrocarbon-extracting liquids can apply to other methods of
hydrocarbon recovery to obtain the advantages provided by the
present invention.
[0104] In another aspect, a method for optimizing a turpentine
liquid for extraction of hydrocarbon-containing organic matter from
hydrocarbon containing matter is provided. Generally, the method
includes providing a sample of the hydrocarbon-containing material
and analyzing the hydrocarbon material to determine the type of
hydrocarbon being extracted. A formulation for extraction of
hydrocarbon-containing organic matter from the hydrocarbon material
is provided, wherein the formulation is a function of the type of
formation, general operating conditions, and the size of the
particulate hydrocarbon material. Generally, the formulation
includes at least about 40% by volume .alpha.-terpineol and at
least about 10% by volume .beta.-terpineol. The amount of
.alpha.-terpineol and .beta.-terpineol in the formulation is then
adjusted based upon the parameters noted above. In general, while
the above noted method provides a good starting point for
determining the desired formulation for extraction of various
hydrocarbon containing materials, for other hydrocarbon-containing
materials and under specified operating conditions, either a series
of statistically designed experiments or a series of experiments
according to an optimization method can be performed to determine
the optimum composition of the liquid turpentine.
[0105] As shown in Table 1, the specific formulation for
extraction, liquefaction and/or solubilization of
hydrocarbon-containing organic matter from tar sands varies based
upon the particle size. In certain embodiments, the method for
preparing a turpentine liquid for extracting hydrocarbon-containing
organic matter from tar sands includes adjusting the amount of
.alpha.-terpineol and .beta.-terpineol in the formulation as a
function of the size of the hydrocarbon rich solid particulate
being extracted. In other embodiments, if the
hydrocarbon-containing organic particulate matter includes low
grade coal or an oil shale, the amount .alpha.-terpineol in the
turpentine liquid is increased and the amount of .beta.-terpineol
in the turpentine liquid is decreased. In other embodiments, if the
hydrocarbon-containing organic particulate matter includes tar
sands, the amount .alpha.-terpineol in the turpentine liquid is
decreased and the amount of .beta.-terpineol in the turpentine
liquid is increased. In other embodiments, if the
hydrocarbon-containing organic particulate matter includes tar
sands and the mean diameter of the particulate matter is less than
about 4.76 mm, then the amount .alpha.-terpineol in the turpentine
liquid is decreased and the amount of .beta.-terpineol in the
turpentine liquid is increased. In other embodiments, if the
hydrocarbon-containing organic particulate matter includes tar
sands and the mean diameter of the particulate matter is greater
than about 25 mm (1 mesh), then the amount .alpha.-terpineol in the
turpentine liquid is decreased and the amount of .beta.-terpineol
in the turpentine liquid is increased.
TABLE-US-00001 TABLE 1 Formulations for Extraction of Tar Sands
based upon Particle Size Particle Size .alpha.- .beta.-
.alpha.-/.beta.- (mm diameter) terpineol terpineol terpene other
<5 mm 30-50% vol 35-55% vol 10% vol 5% vol 5 mm-25 mm 40-60% vol
30-50% vol 10% vol 5% vol >25 mm 50-70% vol 25-45% vol 10% vol
5% vol
[0106] Similar to what is shown above with respect to the
extraction of tar sands, as shown in Tables 2 and 3, the
formulation for extraction, liquefaction and/or solubilization of
coal depends on particle size, quality of the coal being extracted,
and general operating conditions. In one embodiment of the method
for preparing a turpentine liquid for extracting
hydrocarbon-containing organic matter, if the
hydrocarbon-containing matter includes anthracite, bituminous coal,
or other high grade coal and the mean diameter of the particulate
matter is less than about 0.1 mm, then the amount of
.alpha.-terpineol in the turpentine liquid is decreased and the
amount of .beta.-terpineol in the turpentine liquid is increased.
In other embodiments, if the hydrocarbon rich particulate matter
includes anthracite, bituminous coal, or other high grade coal and
the mean diameter of the particulate matter is greater than about 1
mm, then the amount of .alpha.-terpineol in the turpentine liquid
is decreased and the amount of .beta.-terpineol in the turpentine
liquid is increased. In another embodiment, if the hydrocarbon rich
particulate matter includes low grade coal and the mean diameter of
the particulate matter is less than about 0.07 mm, then the amount
of .alpha.-terpineol in the turpentine liquid is decreased and the
amount of .beta.-terpineol in the turpentine liquid is increased.
In another embodiment, if the hydrocarbon rich particulate matter
includes low grade coal and the mean diameter of the particulate
matter is greater than about 0.4 mm, then the amount of
.alpha.-terpineol in the turpentine liquid is decreased and the
amount of .beta.-terpineol in the turpentine liquid is
increased.
TABLE-US-00002 TABLE 2 Formulations for Extraction of High Grade
Coal based upon Particle Size Particle Size .alpha.- .beta.-
.alpha.-/.beta.- (mm diameter) terpineol terpineol terpene other
<0.15 mm 45-65% vol 35-45% vol 10% vol 0% vol 0.8 mm-0.15 mm
50-70% vol 20-40% vol 10% vol 0% vol >0.8 mm 60-80% vol 15-35%
vol 10% vol 0% vol
TABLE-US-00003 TABLE 3 Formulations for Extraction of Low Grade
Coal based upon Particle Size Particle Size .alpha.- .beta.-
.alpha.-/.beta.- (mm diameter) terpineol terpineol terpene other
<0.07 mm 60-80% vol 10-30% vol 5% vol 0% vol 0.07 mm-0.4 mm
70-90% vol 5-25% vol 5% vol 0% vol >0.4 mm 75-95% vol 0-20% vol
5% vol 0% vol
[0107] Similar to what is shown above with respect to the
extraction of tar sands and coal, as shown in Table 4, the
formulation for extraction, liquefaction and/or solubilization of
oil shale depends on particle size. In one embodiment of the method
for preparing a composition for extracting hydrocarbon-containing
organic matter, if the hydrocarbon rich particulate matter includes
an oil shale and the mean diameter of the particulate matter is
less than about 0.074 mm, then the amount of .alpha.-terpineol in
the turpentine liquid is decreased and the amount of
.beta.-terpineol in the turpentine liquid is increased. In another
embodiment, if the hydrocarbon rich particulate matter includes oil
shale and the mean diameter of the particulate matter is greater
than about 0.42 mm, then the amount of .alpha.-terpineol in the
turpentine liquid is decreased and the amount of .beta.-terpineol
in the turpentine liquid is increased.
TABLE-US-00004 TABLE 4 Formulations for Extraction of Oil Shale
based upon Particle Size Particle Size .alpha.- .beta.-
.alpha.-/.beta.- (mm diameter) terpineol terpineol terpene other
<0.07 mm 60-80% vol 10-30% vol 5% vol 0% vol 0.07 mm-0.4 mm
70-90% vol 5-25% vol 5% vol 0% vol >0.4 mm 75-95% vol 0-20% vol
5% vol 0% vol
[0108] The formulation for the extraction of crude oil similarly
depends on the type of crude oil being extracted, liquefied, and/or
solubilized. As shown in Table 5, the formulation for the
extraction, liquefaction and/or solubilization of crude oil is a
function of both pore size and the quality of the density of the
crude oil being extracted. The method includes providing a
turpentine liquid formulation that includes at least about 50% by
volume .alpha.-terpineol and at least about 20% by volume
.beta.-terpineol; adjusting the amount of .alpha.-terpineol and
.beta.-terpineol in the turpentine liquid formulation based upon
the density of the liquid hydrocarbon being extracted. In one
embodiment, if the API gravity of the liquid hydrocarbon being
extracted is greater than about 22.degree., then the amount of
.alpha.-terpineol in the turpentine liquid is decreased and the
amount of .beta.-terpineol in the turpentine liquid is increased.
In another embodiment, if the API gravity of the liquid hydrocarbon
being extracted is less than about 22, then the amount of
.alpha.-terpineol in the turpentine liquid is increased and the
amount of .beta.-terpineol in the turpentine liquid is decreased.
As used herein, light oils have an API of at least about
31.degree., medium crude oils have an API of between about
22.degree. and about 31.degree., heavy oil has an API of between
about 10.degree. and about 22.degree., and extra heavy oil has an
API of less than about 10.degree..
TABLE-US-00005 TABLE 5 Formulations for Extraction of Crude Oil
based upon API Density .alpha.- .beta.- .alpha.-/.beta.- Crude Type
terpineol terpineol terpene other Light/medium 40-70% vol 30-40%
vol 10% vol 10% vol crude (API greater than 22.degree.) Heavy/Extra
50-70% vol 20-35% vol 10% vol 5% vol Heavy (API less than
22.degree.)
[0109] In another aspect, a method for preparing a turpentine
liquid for enhancing recovery of liquid hydrocarbon-containing
organic matter from a sub-surface formation is provided. The method
includes providing a formulation comprising at least about 50% by
volume .alpha.-terpineol and at least about 20% by volume
.beta.-terpineol, and adjusting the amount of .alpha.-terpineol and
.beta.-terpineol in the formulation based upon the geological
features of the sub-surface formation.
[0110] In another aspect, a composition for cleaning and/or
recovering hydrocarbons from a liquid hydrocarbon-containing vessel
is provided, wherein the composition includes at least one compound
selected from natural turpentine, synthetic turpentine, mineral
turpentine, pine oil, .alpha.-pinene, .beta.-pinene,
.alpha.-terpineol, .beta.-terpineol, .gamma.-terpineol, terpene
resins, .alpha.-terpene, .beta.-terpene, .gamma.-terpene, or
mixtures thereof. In other embodiments, the composition for
cleaning and/or recovering hydrocarbons includes at least one
compound selected from geraniol, 3-carene, dipentene
(p-mentha-1,8-diene), nopol, pinane, 2-pinane hydroperoxide, terpin
hydrate, 2-pinanol, dihydromycenol, isoborneol, p-menthan-8-ol,
.alpha.-terpinyl acetate, citronellol, p-menthan-8-yl acetate,
7-hydroxydihydrocitronellal, menthol, and mixtures thereof. In yet
other embodiments, the composition for cleaning and/or recovering
hydrocarbons includes at least one compound selected from anethole,
camphene; p-cymene, anisaldeyde, 3,7-dimethyl-1,6-octadiene,
isobornyl acetate, ocimene, alloocimene, alloocimene alcohols,
2-methoxy-2,6-dimethyl-7,8-epoxyoctane, camphor, citral,
7-methoxydihydro-citronellal, 10-camphorsulphonic acid,
cintronellal, menthone, and mixtures thereof. In one embodiment,
the composition includes at least one compound from the following:
.alpha.-pinene, .beta.-pinene, .alpha.-terpineol, and
.beta.-terpineol. In another embodiment, the composition includes
at least about 25% by volume .alpha.-terpineol or
.beta.-terpineol.
[0111] In another aspect, a method for cleaning and/or recovering
hydrocarbons from a liquid hydrocarbon-containing vessel is
provided. The method includes contacting the interior of vessel
with a hydrocarbon cleaning composition that includes at least one
compound selected from .alpha.-pinene, .beta.-pinene,
.alpha.-terpineol, and .beta.-terpineol to create a mixture,
wherein the mixture includes the liquid hydrocarbon residue and the
hydrocarbon cleaning composition. The mixture is recovered and
removed from the vessel. In certain embodiments, the cleaning
composition includes at least about 25% by volume of
.alpha.-terpineol or .beta.-terpineol. In certain other
embodiments, the cleaning composition includes at least about 25%
by volume of .alpha.-terpineol and at least about 25% by volume
.beta.-terpineol.
[0112] In one embodiment, the present invention provides a method
of extracting hydrocarbon-containing organic matter from a
hydrocarbon-containing material, comprising extracting the
hydrocarbon-containing organic matter by a process comprising,
consisting essentially of, or consisting of providing a
substantially surfactant-free first liquid comprising a non-aqueous
hydrocarbon-extracting liquid consisting essentially of a
turpentine liquid, contacting the hydrocarbon-containing material
with the non-aqueous hydrocarbon extracting liquid such that an
extraction mixture is formed, the extraction mixture comprising at
least a portion of the hydrocarbon-containing organic matter
extracted into the non-aqueous hydrocarbon extracting liquid, and
separating the extraction mixture from any residual material
containing non-soluble material from the hydrocarbon-containing
material that is not soluble in the non-aqueous hydrocarbon
extracting liquid.
[0113] In a further embodiment, the hydrocarbon-containing organic
matter contacts the hydrocarbon-extracting liquid in situ in an
underground formation containing hydrocarbon-containing organic
matter, and means are provided for extracting
hydrocarbon-containing organic matter from an underground
formation.
[0114] In a further embodiment, the extraction mixture can be
separated into a first portion and a second portion, the first
portion of the extraction mixture comprising a hydrocarbon product
comprising at least a portion of the hydrocarbon-containing organic
matter, the second portion of the extraction mixture comprising at
least a portion of the hydrocarbon-extracting liquid.
[0115] In one embodiment, the amount of organic matter extracted
from the hydrocarbon-containing material is at least about 50%. In
another embodiment, at least about 70% of organic matter is
extracted from the hydrocarbon-containing material. In a further
embodiment from about 75-100% of organic matter is extracted from
the hydrocarbon-containing material.
[0116] In another embodiment, for example when the material is
super heavy crude oil e.g. Venezuelan extra heavy crude, the
methods of the present invention are operable to extract at least
about 30-35% of the amount of organic matter from the
hydrocarbon-containing material.
[0117] In a further embodiment, at least about 80% of hydrocarbons
present in a hydrocarbon-containing material and extractable in the
non-aqueous hydrocarbon extracting liquid can be extracted into the
non-aqueous hydrocarbon extracting liquid within about 5 minutes of
contacting. In other embodiments, at least about 80% of
hydrocarbons present in a hydrocarbon-containing material and
extractable in the non-aqueous hydrocarbon extracting liquid can be
extracted into the non-aqueous hydrocarbon extracting liquid within
about 3 minutes of contacting.
[0118] In one embodiment, the hydrocarbon-containing material is
contacted with hydrocarbon-extracting liquid in a ratio of at least
2:1 of turpentine liquid to hydrocarbon-containing material.
[0119] In certain embodiments with extraction, e.g., from coal, the
hydrocarbons being extracted are predominantly from the volatiles
portion of the coal, as opposed to fixed carbon in the coal.
[0120] In one embodiment, the hydrocarbon-containing material can
be a natural hydrocarbon-containing material from a naturally
occurring geological formation. Some examples of natural
hydrocarbon-containing materials are coal, crude oil, tar, tar
sands, oil shale, oil sands, natural gas, petroleum gas, crude
bitumen, natural kerogen, natural asphalt, and natural
asphaltene.
[0121] In one embodiment of the method, the hydrocarbon-containing
organic matter is extracted into the hydrocarbon-extracting liquid
in an amount that corresponds to an amount of from about 1% to
about 100% of the hydrocarbon-containing organic matter originally
contained within the natural hydrocarbon-containing material. In
certain embodiments, at least about 40 or 50%, in one embodiment at
least about 60%, in another embodiment at least about 70%, in yet
another embodiment at least about 80%, and in another embodiment at
least about 90% of the hydrocarbon-containing organic matter
originally contained within the natural hydrocarbon-containing
material can be extracted into the hydrocarbon extracting liquid.
Extraction of some or all of the hydrocarbon-containing organic
matter from the natural hydrocarbon-containing material into the
hydrocarbon-extracting liquid can take place from about 3 seconds
to 180 minutes of contacting, between from about 97 seconds and 30
minutes, or between from about 15 and 30 minutes, in one embodiment
within less than about 10 minutes, in another embodiment within
less than about 5 minutes, in another embodiment within from 3
seconds to about 3 minutes at a contacting temperature in a range
of from about 10 to 400.degree. C., in one embodiment less than
100.degree. C., in another embodiment in a range of from about
20-30.degree. C. at a weight ratio of hydrocarbon-extracting liquid
to the natural hydrocarbon-containing material of from about 10% to
about 600%. In another embodiment the weight ratio of
hydrocarbon-extracting liquid to the natural hydrocarbon-containing
material is from about 1:1 to 2:1.
[0122] In one embodiment, hydrocarbon-containing organic matter
from coal is extracted into the hydrocarbon-extracting liquid in an
amount that corresponds to an amount of from about 60 to 100% of
the hydrocarbon-containing organic matter originally contained
within the coal sample and/or total carbon of at least from about
30% to 90% of hydrocarbon-containing organic matter originally
contained within the coal sample within about 3 seconds to 3
minutes of contacting at a contacting temperature in a range of
from about 80 to 100.degree. C. at a weight ratio of
hydrocarbon-extracting liquid to the coal of from about 1:1 to
2:1.
[0123] In another embodiment, hydrocarbon-containing organic matter
from tar sands is extracted into the hydrocarbon-extracting liquid
in an amount that corresponds to an amount of from about 85 to 100%
of the hydrocarbon-containing organic matter originally contained
within the tar sands sample within about 3 seconds to 3 minutes of
contacting at a contacting temperature in a range of from about 30
to 60.degree. C. at a weight ratio of hydrocarbon-extracting liquid
to the tar sands of from about 1:1 to 2:1.
[0124] In another embodiment, hydrocarbon-containing organic matter
from oil shale is extracted into the hydrocarbon-extracting liquid
in an amount that corresponds to an amount of from about 50 to 100%
of hydrocarbon-containing organic matter originally contained
within the oil shale sample within about 3 seconds to 3 minutes of
contacting at a contacting temperature in a range of from about 100
to 130.degree. C. at a weight ratio of hydrocarbon-extracting
liquid to the oil shale of from about 1:1 to 2:1.
[0125] In another embodiment, crude oil in an underground formation
is contacted with hydrocarbon-extracting liquid in situ in the
underground formation. During contacting, hydrocarbon-containing
organic matter from the crude oil extracted into the
hydrocarbon-extracting liquid in an amount that corresponds to an
amount of from about 80 to 100% of hydrocarbon-containing organic
matter originally contained within the crude oil sample within
about 3 seconds to 3 minutes of contacting at a ratio of from about
1:1 to 1:2 of the hydrocarbon-extracting liquid to total pore
volume of the underground formation.
[0126] In another embodiment, hydrocarbon-containing organic matter
from natural gas is extracted into the hydrocarbon-extracting
liquid in an amount that corresponds to an amount of from about 50
to 100% of hydrocarbon-containing organic matter originally
contained within the natural gas sample within from about 3 seconds
to 60 minutes of contacting at a contacting temperature in a range
of from about 10 to 300.degree. C. at a weight ratio of
hydrocarbon-extracting liquid to said hydrocarbon-containing
material of from about 0.1 to 600%.
[0127] In another embodiment, the present invention provides a
method for modifying sulfur compounds in a sulfur-containing
hydrocarbon-containing material from a natural geological formation
by contacting or mixing the hydrocarbon-containing material with
the hydrocarbon-extracting liquid such that the interaction of the
turpentine liquid with sulfur in the hydrocarbon-containing
material is operable to modify the hydrocarbon-containing material
e.g. by inhibiting the corrosive and toxic effects of a reactive
sulfur species. Further, this embodiment of the invention can be
applied to sweetening a gas. Sweetening is accomplished through use
of a sweetening module of a gas processing plant and may include
trays, packing, or the like.
[0128] Sulfur-containing hydrocarbon-containing materials can
include, but are not limited to, natural gas, petroleum gas, crude
oil, tar sands, oil shale, and coal. The sulfur may be present as
elemental sulfur, hydrogen sulfide, sulfides, disulfides,
mercaptans, thiophenes, benzothiophenes, and the like.
[0129] In a further embodiment, sulfur-containing hydrocarbon
containing materials in a gaseous form, such as natural gas or
petroleum gas, can be bubbled through the hydrocarbon-extracting
liquid to sweeten the gas.
[0130] In one embodiment, the present invention provides a method
of reducing the corrosion of a corrodible surface. During
transportation, drilling, downhole operations, exploration,
hydrocarbon production, storage, handling, or production of
hydrocarbon-containing material, for example by pipelines, tankers,
casings, fishing tools, or drill bits, the metal surfaces that
contact sulfur-containing compounds in the hydrocarbon containing
materials may corrode. The present invention provides a method for
significantly reducing corrosion by the addition of a
corrosion-reducing liquid to a hydrocarbon-containing material.
Uniform and pitting corrosion can be inhibited by the methods of
the present invention. When a hydrocarbon-containing material is
mixed with the corrosivity-reducing liquid thereby forming a
mixture, the corrosion rate of the corrodible surfaces contacted
with the mixture is substantially reduced as compared to corrosion
of these surfaces when contacted with hydrocarbon-containing
material in the absence of the corrosion-reducing liquid. In one
embodiment, the corrosivity-reducing liquid does not produce a
stable sulfonated component. In another embodiment, sulfur does not
accumulate in the turpentine extraction liquid.
[0131] In some embodiments, the mixture comprises at least from
about 0.0001 to 0.002% by volume of the corrosivity-reducing
liquid. In another embodiment, the mixture comprises at least from
about 0.0005% by volume of the corrosivity-reducing liquid. In a
further embodiment, the mixture comprises at least from about
0.001% by volume of the corrosivity-reducing liquid. In a further
embodiment, the mixture comprises at least from about 0.0015% by
volume of the corrosivity-reducing liquid. In a further embodiment,
the mixture comprises at least from about 0.001% to 0.002% by
volume of the corrosivity-reducing liquid. In another embodiment,
the mixture comprises at least from about 0.01% to 10% by volume of
the corrosivity-reducing liquid. In a further embodiment, the
mixture comprises at least from about 0.1% to 5% by volume of the
corrosivity-reducing liquid. In yet another embodiment, the mixture
comprises at least from about 0.5% to 2% by volume of the
corrosivity-reducing liquid. In a further embodiment, the mixture
comprises at least from about 1% by volume of the
corrosivity-reducing liquid.
[0132] In a further embodiment, the rate of corrosion is reduced by
at least about 2-fold as compared to corrosion of the surface when
contacted with a hydrocarbon-containing material in an absence of
the corrosivity-reducing liquid.
[0133] In another embodiment the rate of corrosion is reduced by at
least about 3-fold. In a further embodiment, the rate of corrosion
is reduced by at least about 4-fold as compared to corrosion of the
surface when contacted with a hydrocarbon-containing material in an
absence of the corrosivity-reducing liquid.
[0134] In one embodiment, the corrosivity-reducing liquid includes
.alpha.-terpineol, .beta.-terpineol, .beta.-pinene, and p-cymene.
In another embodiment the corrosivity-reducing liquid includes
about 40% to about 60% .alpha.-terpineol, about 30% to about 40%
.beta.-terpineol, about 5% to about 20% .beta.-pinene, and about 0
to about 10% p-cymene. In a further embodiment, the
corrosivity-reducing liquid comprises a blend of turpentine
liquids.
[0135] In certain embodiments, the hydrocarbon-containing material
treated with corrosivity-reducing liquid is crude oil, heavy crude
oil, tar sands, oil sands, oil shale, natural gas, petroleum gas,
or a combination thereof.
[0136] In another embodiment, the present invention provides a
method of preparing a hydrocarbon-containing gas by contacting a
hydrocarbon-containing material with a substantially
surfactant-free first liquid that includes a non-aqueous
hydrocarbon-extracting liquid, wherein the non-aqueous
hydrocarbon-extracting liquid includes a turpentine liquid, forming
a mixture, wherein the mixture comprises at least a portion of the
hydrocarbon-containing organic matter extracted into the
hydrocarbon-extracting liquid, and heating the mixture to form a
gas containing the hydrocarbon-extracting material and hydrocarbons
extracted from the hydrocarbon-containing material.
[0137] In certain embodiments, the hydrocarbon-containing material
is crude oil, heavy crude oil, tar sands, oil sands, oil shale,
natural gas, petroleum gas, or a combination thereof.
[0138] The present invention provides a method for increasing
recovery of hydrocarbon-containing organic matter from a production
well coupled to a hydrocarbon-containing sub-surface formation
containing hydrocarbon-containing material. The method includes:
providing an injection well in fluid communication with the
sub-surface formation, injecting a substantially surfactant-free
first liquid comprising a non-aqueous hydrocarbon-extracting liquid
consisting essentially of a turpentine liquid, e.g. terpineol, into
the formation to form an extraction mixture comprising at least a
portion of the extraction mixture hydrocarbon-containing organic
matter in at least a portion of the turpentine liquid, recovering
the extraction mixture from the formation through the production
well, and separating the extraction mixture to produce a
hydrocarbon product stream and a turpentine liquid stream. The
hydrocarbon-extracting liquid can be recycled for reinjection.
[0139] The present invention provides a method for recovering
hydrocarbon-containing organic matter from tar sands. The method
involves obtaining tar sands comprising recoverable
hydrocarbon-containing organic matter, providing a substantially
surfactant-free first liquid comprising a hydrocarbon-extracting
liquid comprising a turpentine liquid comprising at least one of
.alpha.-terpineol or .beta.-terpineol, supplying the tar sands
sample to a contacting vessel, contacting the tar sands sample with
the hydrocarbon-extracting liquid in a contacting vessel and
agitating the tar sands sample with the hydrocarbon-extracting
liquid such that an extraction mixture is formed and a residual
material is formed. separating the extraction mixture from the
residual material, separating the extraction mixture into a
hydrocarbon product stream and a hydrocarbon-extracting liquid
stream, and recycling at least a portion of the
hydrocarbon-extracting liquid stream to the contacting step. The
extraction mixture includes at least a portion of the
hydrocarbon-containing organic matter in the hydrocarbon-extracting
liquid and the residual material includes at least a portion of
non-soluble material from the tar sands that is not soluble in the
hydrocarbon-extracting liquid and the hydrocarbon product stream
includes at least a portion of the hydrocarbon-containing organic
matter from the tar sands.
[0140] The present invention provides a method for recovering
hydrocarbon-containing organic matter from comminuted
hydrocarbon-containing oil shale. The method involves contacting
the comminuted hydrocarbon-containing oil shale with a
substantially surfactant-free first liquid comprising a non-aqueous
hydrocarbon-extracting liquid consisting essentially of a
turpentine liquid selected from the group consisting of natural
turpentine, synthetic turpentine, mineral turpentine, pine oil,
.alpha.-pinene, .beta.-pinene, .alpha.-terpineol, .beta.-terpineol,
.gamma.-terpineol, terpene resins, .alpha.-terpene, .beta.-terpene,
.gamma.-terpene, geraniol, 3-carene, dipentene
(p-mentha-1,8-diene), nopol, pinane, 2-pinane hydroperoxide, terpin
hydrate, 2-pinanol, dihydromycenol, isoborneol, p-menthan-8-ol,
.alpha.-terpinyl acetate, citronellol, p-menthan-8-yl acetate,
7-hydroxydihydrocitronellal, menthol, anethole, camphene; p-cymene,
anisaldeyde, 3,7-dimethyl-1,6-octadiene, isobornyl acetate,
ocimene, alloocimene, alloocimene alcohols,
2-methoxy-2,6-dimethyl-7,8-epoxyoctane, camphor, citral,
7-methoxydihydro-citronellal, 10-camphorsulphonic acid,
cintronellal, menthone, and mixtures thereof, filtering the
comminuted hydrocarbon-containing oil shale, feeding the crushed
hydrocarbon-containing oil shale to a contacting vessel, contacting
the comminuted hydrocarbon-containing oil shale with the
hydrocarbon-extracting liquid such that an extraction mixture is
formed and a residual material is formed, separating the extraction
mixture from the residual material, separating the
hydrocarbon-containing organic matter from the
hydrocarbon-extracting liquid in the extraction mixture to produce
a hydrocarbon product stream and a hydrocarbon-extracting liquid
stream, the hydrocarbon product stream comprising at least a
portion of the hydrocarbon-containing organic matter from the
comminuted hydrocarbon containing oil shale, and recycling at least
a portion of the hydrocarbon-extracting liquid stream to the
contacting step. The extraction mixture comprising at least a
portion of the hydrocarbon-containing organic matter in the
hydrocarbon-extracting liquid, the residual material comprising at
least a portion of non-soluble material from the oil shale that is
not soluble in the hydrocarbon-extracting liquid
[0141] The present invention provides a method for recovering
hydrocarbon-containing organic matter from hydrocarbon-containing
coal rich sub-surface formation. The method involves obtaining and
grinding coal comprising a recoverable hydrocarbon-containing
organic matter to produce crushed coal, filtering the crushed coal,
feeding the crushed coal to a contacting vessel, said contacting
vessel which has at least one inlet for supplying a
hydrocarbon-extracting liquid to the contacting vessel, contacting
the crushed coal with a substantially surfactant-free non-aqueous
hydrocarbon-extracting liquid consisting essentially of a
turpentine liquid selected from the group consisting of natural
turpentine, synthetic turpentine, mineral turpentine, pine oil,
.alpha.-pinene, .beta.-pinene, .alpha.-terpineol, .beta.-terpineol,
.gamma.-terpineol, terpene resins, .alpha.-terpene, .beta.-terpene,
.gamma.-terpene, geraniol, 3-carene, dipentene
(p-mentha-1,8-diene), nopol, pinane, 2-pinane hydroperoxide, terpin
hydrate, 2-pinanol, dihydromycenol, isoborneol, p-menthan-8-ol,
.alpha.-terpinyl acetate, citronellol, p-menthan-8-yl acetate,
7-hydroxydihydrocitronellal, menthol, anethole, camphene; p-cymene,
anisaldeyde, 3,7-dimethyl-1,6-octadiene, isobornyl acetate,
ocimene, alloocimene, alloocimene alcohols,
2-methoxy-2,6-dimethyl-7,8-epoxyoctane, camphor, citral,
7-methoxydihydro-citronellal, 10-camphorsulphonic acid,
cintronellal, menthone, and mixtures thereof such that an
extraction mixture is formed and a residual material is formed, the
extraction mixture comprising at least a portion of the
hydrocarbon-containing organic matter in the hydrocarbon-extracting
liquid, the residual material comprising at least a portion of
non-soluble material from the coal that is not soluble in the
hydrocarbon-extracting liquid, separating the residual material
from the extraction mixture, separating the hydrocarbon-containing
organic matter from the hydrocarbon-extracting liquid to produce a
hydrocarbon product stream and a hydrocarbon-extracting liquid
stream, the hydrocarbon product stream comprising at least a
portion of the hydrocarbon-containing organic matter from the coal,
and recycling at least a portion of the hydrocarbon-extracting
liquid stream to the contacting step, wherein said first liquid
contains no water or essentially no water.
Examples
Example 1
[0142] In this example, coal from the Pittsburgh seam in Washington
County, Pennsylvania was liquefied with reagent .alpha.-terpineol.
The coal sample was obtained from the Coal Bank at Pennsylvania
State University, which provided the following proximate analyses
for it; 2.00 wt. % of as-received moisture, 9.25 wt. % of dry ash,
38.63 wt. % of dry volatile matter, and 50.12 wt. % of dry fixed
carbon. The particle size of coal sample was about 60 mesh. About
60 grams of .alpha.-terpineol was gently added to about 30 grams of
the coal sample placed in an extraction vessel, thus giving rise to
the reagent-to-sample ratio of 2 to 1. The capped, but not tightly
sealed, extraction vessel containing the resultant mixture of
.alpha.-terpineol and coal was maintained at the constant
temperature of about 96.degree. C. and continually agitated.
Without boiling the .alpha.-terpineol, the pressure in the
extraction vessel remained at the ambient pressure of slightly less
than about 1.01.times.10.sup.5 Pascals (1 atm). After about 30
minutes, the mixture was filtered and the coal particles retained
on the filter were washed with ethanol and dried to a constant
weight. On the basis of weight loss, the conversion, i.e., the
extent of liquefaction, of the coal sample was determined to be
about 68 wt. %.
Example 2
[0143] This example is identical to Example 1 in all aspects except
two. After maintaining the temperature at about 96.degree. C., for
about 30 minutes, as done in Example 1, the extraction vessel
containing the coal sample and .alpha.-terpineol was maintained at
a temperature at about 135.degree. C. for an additional period of
about 30 minutes. The pressure in the extraction vessel remained at
the ambient pressure of slightly less than about
1.01.times.10.sup.5 Pascals (1 atm). The conversion, i.e., the
degree of liquefaction, of the coal sample was determined to be
about 70 wt. %.
Example 3
[0144] The coal sample used was from the same source with the same
proximate analyses as those used in the preceding two examples.
About 31 grams of .alpha.-terpineol were added to about 31 grams of
the coal sample in an extraction vessel. The mixture was maintained
at about 96.degree. C. and an ambient pressure of slightly less
than about 1.01.times.10.sup.5 Pascals (1 atm) for about 30
minutes. The conversion, i.e., the degree of liquefaction, of the
coal sample attained was determined to be about 71 wt. % by
weighing the sample after filtering, washing, and drying as done in
the preceding two examples.
Example 4
[0145] This example is identical to Example 3, except that about 30
wt. % of .alpha.-terpineol was replaced with hexane, providing a
reagent that includes 70 wt. % .alpha.-terpineol and 30 wt. %
hexane. This reduced the conversion, i.e., the degree of
liquefaction to about 1.3 wt. %.
Example 5
[0146] The source and proximate analyses of coal sample and
experimental conditions in terms of temperature, pressure and
reagent-to-sample ratio for this example were the same as those of
Example 3. The duration of the extraction, however, was reduced
from about 30 minutes to about 20 minutes. Additionally, about 30
wt. % of the .alpha.-terpineol was replaced with 1-butanol,
providing a reagent that includes 70 wt. % .alpha.-terpineol and 30
wt. % 1-butanol. The amount of coal liquefied was only about 0.30
gram, corresponding to conversion of about 1.0 wt. %.
Example 6
[0147] This example is the same as Example 3 in terms of the source
and proximate analyses of coal sample and temperature, pressure and
duration of the extraction. The amount of the coal sample used was,
however, about 25 grams and the reagent comprised about 24 grams
(80 wt. %) of .alpha.-terpineol and about 6 grams (20 wt. %) of
xylenes, providing a reagent that includes 70 wt. %
.alpha.-terpineol and 30 wt. % xylenes. The coal liquefied was
about 10.0 grams, corresponding to conversion of about 40 wt.
%.
Example 7
[0148] In this example, coal from the Wyodak seam in Campbell
County, Wyoming was liquefied with reagent .alpha.-terpineol. The
coal sample was obtained from the Coal Bank at Pennsylvania State
University, which provided the following proximate analyses for it;
26.30 wt. % of as-received moisture, 7.57 wt. % of dry ash, 44.86
wt. % of dry volatile matter, and 47.57 wt. % of dry fixed carbon.
The coal sample's particle size was about 20 mesh. About 60 grams
of .alpha.-terpineol was gently added to about 30 grams of the coal
sample placed in an extraction vessel, a reagent-to-sample ratio of
about 2 to 1. The capped, but not tightly sealed, extraction vessel
containing the resultant mixture of .alpha.-terpineol and coal was
maintained at a constant temperature of about 96.degree. C. and
continually agitated. Without boiling of the .alpha.-terpineol, the
pressure in the extraction vessel remained at the ambient pressure
of slightly less than about 1.01.times.10.sup.5 Pascals (1 atm).
After about 30 minutes, the mixture in the extraction vessel was
filtered and the coal particles retained on the filter were washed
with ethanol and dried to a constant weight. On the basis of weight
loss, the conversion, i.e., the degree of liquefaction, of the coal
sample was determined to be 75 wt. %.
Example 8
[0149] The experiment in this example was carried out under the
conditions identical to those of the preceding example except one.
About 15 grams of .alpha.-terpineol were added, instead of about 60
grams, as done in the preceding example, to about 30 grams of the
coal sample, thus attaining the reagent-to-coal ratio of 0.5 to 1.
The conversion, i.e., the degree of liquefaction, of the coal
sample attained decreased from about 75 wt. %, attained in the
preceding example, to about 69 wt. %.
Example 9
[0150] In this example, about 3 grams of oil shale from the
Green-river region of Colorado was solubilized with about 9 grams
of .alpha.-terpineol, thus giving rise to the reagent-to-sample
ratio of 3 to 1, to extract kerogen (organic matter) and/or bitumen
(organic matter) from it. The organic carbon content, including
both volatile and fixed carbon, was determined to be about 22.66
wt. % by a certified analysis company. Two experiments with the
oil-shale samples, having the particle size of 60 mesh, were
carried out under the ambient temperature and pressure of about
25.degree. C. and slightly less than about 1.01.times.10.sup.5
Pascals (1 atm), respectively. The weight losses of the samples
were determined by weighing after filtering, washing with ethanol,
and drying. These losses were about 9 wt. % after about 30 minutes
and about 17 wt. % after about 45 minutes. From these weight
losses, the conversion, i.e., the degree of extraction of organic
matter, i.e., kerogen and/or bitumen, was estimated to be about 40
wt. % for the former and was about 75 wt. % for the latter.
Example 10
[0151] This example duplicated the preceding example with the
exception that a single experiment, lasting about 15 minutes, was
carried out at the temperature of about 96.degree. C., instead of
about 25.degree. C. The weight loss of the oil shale sample was
about 12 wt. %, corresponding to the conversion, i.e., the degree
of extraction, of kerogen (organic matter) of about 53 wt. %
Example 11
[0152] In this example, bitumen (organic matter) in tar sands from
Alberta, Canada, was solubilized and extracted with commercial
grade synthetic turpentine. The tar-sands sample was obtained from
Alberta Research Council, which provided the following proximate
analyses for it; 84.4 wt. % of dry solids, 11.6 wt. % of dry
bitumen, and 4.0 wt. % of as-received moisture. About 30 grams of
synthetic turpentine were gently added to about 15 grams of the
tar-sands sample in a capped, but not tightly sealed, extraction
vessel, utilizing a reagent-to-sample ratio of about 2 to 1 by
weight. This extraction vessel, containing the resultant mixture of
synthetic turpentine and tar sands, was maintained at a constant
temperature of about 96.degree. C. and continually agitated.
Without boiling of the synthetic turpentine, the pressure in the
extraction vessel remained at the ambient pressure of slightly less
than about 1.01.times.10.sup.5 Pascals (1 atm). After about 20
minutes, the mixture in the extraction vessel was filtered and the
solids (tar sands) retained on the filter were washed with ethanol
and dried to a constant weight. On the basis of weight loss, the
conversion, i.e., the degree of extraction, of bitumen from the
tar-sands sample was determined to be about 100 wt. %.
Example 12
[0153] In this example, about 60 grams of the tar-sands sample from
the same source with the same proximate analyses as those of the
preceding example were extracted by about 60 grams of
.alpha.-terpineol, instead of commercial-grade synthetic
turpentine, which includes .alpha.-terpineol. The resultant
reagent-to-sample ratio was 1 to 1 instead of 2 to 1 as in the
preceding example. The experiment lasted about 30 minutes at the
temperature of about 96.degree. C. under the ambient pressure of
slightly less than about 1.01.times.10.sup.5 Pascals (1 atm). The
conversion, i.e., the extent of extraction, of bitumen (organic
matter) in the tar-sands sample was determined to be about 100 wt.
%.
Example 13
[0154] In this example, about 60 grams of the tar-sands sample from
the same source with the same proximate analyses as those of the
preceding two examples were extracted by about 60 grams of
synthetic turpentine, which is of the commercial grade. The
resultant reagent-to-sample ratio, therefore, was about 1 to 1. The
experiment was carried out for about 30 minutes at the temperature
of about 96.degree. C. under the ambient pressure of slightly less
than about 1.01.times.10.sup.5 Pascals (1 atm). The conversion,
i.e., the degree of extraction, of bitumen (organic matter) in the
tar-sands sample was determined to be about 70 wt. %.
Example 14
[0155] The experiment in this example duplicated that in Example 8
in all aspects except that the reagent-to-sample ratio was reduced
from about 2 to 1 to about 0.5 to 1: About 60 grams to the
tar-sands sample was extracted by about 30 grams of synthetic
turpentine, which is of the commercial grade. The conversion, i.e.,
the degree of extraction, of bitumen (organic matter) decreased
from about 100 wt. % attained in Example 9 to about 70 wt. %.
Example 15
[0156] The experiment in this example repeated that of the
preceding example with .alpha.-terpineol instead of the
commercial-grade synthetic turpentine. The conversion, i.e., the
degree of extraction, of bitumen (organic matter) in the tar-sands
sample was about 70 wt. % as in the preceding example.
Example 16
[0157] The experiment in this example was carried out under the
ambient pressure of slightly less than about 1.01.times.10.sup.5
Pascals (1 atm) with the tar-sands sample from the same source with
the same proximate analyses as those in the preceding examples with
tar sands. About 60 grams of commercial-grade synthetic turpentine
was added to about 60 grams of the tar-sands sample, thus giving
rise to the reagent-to-sample ratio of about 1 to 1. The
temperature of the sample and commercial-grade synthetic turpentine
was maintained at about 65.degree. C. for about 30 minutes followed
by cooling to about 15.degree. C. within about 5 minutes.
Subsequently, the tar-sands sample was filtered, washed, dried and
weighed. On the basis of weight loss, the conversion, i.e., the
degree of extraction, of bitumen (organic matter) in the tar-sands
sample was determined to be about 70 wt. %.
Example 17
[0158] The experiment in this example repeated that of the
preceding example with .alpha.-terpineol instead of commercial
grade synthetic turpentine. The conversion, i.e., the degree of
extraction, of bitumen (organic matter) increased to about 90 wt. %
from about 70 wt. % of the preceding examples.
Example 18
[0159] In this example, a tar-sands sample, weighing about 30
grams, from the same source with the same proximate analyses as
those in Examples 11 through 17, was extracted with a liquid that
included about 20 grams (80 wt. %) of .alpha.-terpineol and about 5
grams (20 wt. %) of toluene at the temperature of about 96.degree.
C. under the ambient pressure of slightly less than about
1.01.times.10.sup.5 Pascals (1 atm). The duration of the experiment
(reaction or extraction time) was about 30 minutes. The weigh loss
of the sample was about 10.2 grams. From this weigh loss, the
conversion, i.e., the degree of extraction, of bitumen (organic
matter) was estimated to be about 33 wt. %.
Example 19
[0160] Three tar-sands samples, all from the same source with the
same proximate analyses as those used in all preceding examples
with tar sands were extracted by reagents comprising various
amounts of .alpha.-terpineol and ethanol at the temperature of
about 15.degree. C. under the ambient pressure of slightly less
than about 1.01.times.10.sup.5 Pascals (1 atm). The duration of
each experiment (reaction or extraction time) was about 15 minutes
for each tar-sands sample. The first sample was extracted with a
mixture comprising about 0 gram (0 wt. %) of .alpha.-terpineol and
about 15 grams (100 wt. %) of ethanol, i.e., with pure ethanol. The
second sample was extracted with a mixture comprising about 7.5
grams (50 wt. %) of .alpha.-terpineol and about 7.5 grams (50 wt.
%) of ethanol. The third sample was extracted with a mixture
comprising about 12 grams (80 wt. %) of .alpha.-terpineol and about
3 grams (20 wt. %) of ethanol. The weight losses and the estimated
conversions, i.e., the degrees of extraction, of bitumen (organic
matter) in the three samples were about 0.2 gram (1.0 wt. %), 0.6
gram (3.0 wt. %) and 0.9 gram (4.5 wt. %), for the first, second
and third sample, respectively.
Example 20
[0161] Irregular-shaped pellets of commercial-grade asphalt whose
average size was about 15 mm were solubilized and extracted with
.alpha.-terpineol and at the ambient temperature of about
22.degree. C. under the ambient pressure of slightly less than
about 1.01.times.10.sup.5 Pascals (1 atm). The first sample
weighing about 20 grams was solubilized and extracted with about 40
grams of .alpha.-terpineol, and the second sample also weighing
about 20 grams was solubilized and extracted with about 20 grams of
.alpha.-terpineol. The hydrocarbons in both samples were completely
extracted after 30 minutes. These experiments were carried out to
simulate the solubilization and extraction of heavy crude oil,
which tends to be rich in asphaltenes like asphalt.
Example 21
[0162] In this example, bitumen (organic matter) in tar-sands from
the same source with the same proximate analyses as those used in
all previous examples with tar sands was solubilized and extracted
with two varieties of vegetable oils, soybean oil and corn oil. The
vegetable oils are completely miscible with turpentine liquid. In
the first experiment, a tar-sands sample weighing about 15 grams
was blended and agitated continually with about 30 grams of soybean
oil for about 20 minutes at the temperature of about 96.degree. C.
under the ambient pressure of slightly less than about
1.01.times.10.sup.5 Pascals (1 atm). The weight loss was about 0.5
gram from which the conversion, i.e., the degree of extraction, of
bitumen in the sample was estimated to be about 3.3 wt. %. In the
second experiment, a tar-sands sample weighing about 30 grams was
blended and agitated continually with about 60 grams of corn oil
for about 30 minutes at the temperature of about 175.degree. C.
under the ambient pressure of slightly less than about
1.01.times.10.sup.5 Pascals (1 atm). The weight loss was about 4.8
grams from which the conversion, i.e., the degree of extraction, of
bitumen in the sample was estimated to be about 12 wt. %.
Example 22
[0163] Two tests were performed on Berea sandstone plug core
samples to determine the effect of reagent injection on oil
recovery from core. The first test was designed to determine the
increment oil recovery due to .alpha.-terpineol injection after a
field had already undergone waterflooding to the limit. The
selected core contained 9.01 mL of laboratory oil simulating crude
oil. The waterflooding with aqueous solution containing 3.0% of
potassium chloride produced 4.6 mL of oil. Five (5) pore volumes of
.alpha.-terpineol injection produced additional 3.61 mL of oil,
thereby leaving the core with less than 8.0% of oil remaining in
the original volume. The second test was designed to represent the
increased recovery that could be expected from a virgin reservoir
with .alpha.-terpineol injection. The selected core contained 8.85
mL of laboratory oil simulating crude oil. Oil production began
after approximately 0.5 pore volumes of .alpha.-terpineol
injection, and continued until 3.5 pore volumes of
.alpha.-terpineol had been injected; however, the majority of the
oil was recovered after only 2.5 pore volumes of .alpha.-terpineol
injection. A total of 7.94 mL of laboratory oil was recovered,
thereby leaving the core with less than 7.5% of oil remaining in
the original volume.
[0164] In one experiment, various ratios of a turpentine liquid to
tar sands sample were tested. The turpentine liquid for each of the
experiments provided below had the same formulation, wherein the
composition included about 60% by volume .alpha.-terpineol, about
20% by volume .beta.-terpineol, and about 20% by volume
.gamma.-terpineol. The tar sands were a different mix of ores from
Alberta, Canada, having a bitumen content of approximately 12% by
weight and a water content of between about 4-5% by weight. The
experiments were all performed at various temperatures as listed in
Table 6.
[0165] As shown in Table 6 below, recovery of hydrocarbons from tar
sands across all ratios provided below (i.e., ratios of turpentine
liquid to tar sands ranging from about 1:2 to about 2:1) resulted
in good recovery of hydrocarbons and little discernible difference.
With respect to the temperature at which the extraction is carried
out, it is believed that the optimum temperature for the
extraction, solubilization and/or liquefaction of hydrocarbons from
tar sands is about 65.degree. C. As shown in the table, at about
130.degree. C., the amount of hydrocarbons recovered from the tar
sands is reduced. It is noted however, that for certain solids from
which it is particularly difficult to recover hydrocarbons,
increasing the temperature of the extraction solvent can increase
the amount of hydrocarbons that are recovered. Finally, it is shown
that exposure time had very little effect on the amount of
materials that were extracted. This is likely because the shortest
extraction time was about 20 minutes, which is believed to be more
than adequate for the extraction of the hydrocarbons from tar
sands.
TABLE-US-00006 TABLE 6 Extractable Weight of Ratio of Amount of
Percent Exposure Tar Sands HC extraction tar sands HC HC Temp,
Time, Weight, g weight, g solvent to solvent extracted, g extracted
.degree. C. minutes 15 2.0 30.0 1:2 3.2 161 96 20 60 7.8 120.0 1:2
5.4 69 96 30 60 7.8 31.6 2:1 9.6 123 96 30 60 7.8 60.0 1:1 7.6 97
65 30 60 7.8 60.0 1:1 4.0 51 130 30 60 7.8 60.0 1:1 6.3 80 65
30
[0166] Additional experiments were conducted using alternative
solvents, namely ethanol and corn oil, which was compared with the
composition that included about 60% by volume .alpha.-terpineol,
about 20% by volume .beta.-terpineol, and about 20% by volume
.gamma.-terpineol. As noted in Table 7 provided below, the
performance of ethanol and corn oil were unexpectedly substantially
lower than the composition that included about 60% by volume
.alpha.-terpineol, about 20% by volume .beta.-terpineol, and about
20% by volume .gamma.-terpineol. For example, whereas the terpineol
composition achieved complete or nearly complete extraction of
extractable hydrocarbons, ethanol yielded only about 10% of the
recoverable hydrocarbons and heated corn oil yielded only about 33%
of the recoverable hydrocarbons.
TABLE-US-00007 TABLE 7 Extractable Weight of Ratio of Amount of
Percent Exposure Tar Sands HC extraction tar sands HC HC Temp,
Time, Chemical Weight, g weight, g solvent to solvent extracted, g
extracted .degree. C. minutes Ethanol 15 2.0 15.0 1:1 o.2 10 15 15
Corn oil 30 3.9 60.0 2:1 1.3 33 175 30 60/20/20 60 7.8 60.0 1:1 7.6
97 65 30 terpineol 60/20/20 60 7.8 31.6 2:1 9.6 123 96 30
terpineol
[0167] As shown in Table 8 below, the performance of various
turpentine liquid formulations, including turpentine liquid
formulations that include only .alpha.-terpineol and
.alpha.-terpineol in combination with various known organic
solvents, are provided. The first three compositions presented in
the table include .alpha.-terpineol, .beta.-terpineol, and
.gamma.-terpineol. For example, the first same includes about 60%
by volume .alpha.-terpineol, about 30% by volume .beta.-terpineol,
and about 10% by volume .gamma.-terpineol. The results unexpectedly
show that as the concentration of the .alpha.-terpineol increases,
performance of the turpentine liquid increases to the point that
when the turpentine liquid includes approximately 70%
.alpha.-terpineol, full extraction of the hydrocarbon material from
the tar sands sample is achieved.
[0168] The second set of data is presented for extraction of
hydrocarbon bearing tar sands with pure .alpha.-terpineol. As
shown, extraction of greater than 100% is achieved, likely due to
inconsistencies in the hydrocarbon content of the samples. However,
the results generally demonstrate the unexpected result that
.alpha.-terpineol is capable of extracting substantially all of the
recoverable hydrocarbon from a tar sands sample.
[0169] The data provided in Table 8 illustrates the effectiveness
of mixed systems of .alpha.-terpineol and known organic solvents.
As shown, substantially complete recovery of recoverable
hydrocarbons is achieved with a composition that includes about a
1:1 ratio of .alpha.-terpineol to ethanol. This is unexpected as
pure ethanol only removed about 10% of the total recoverable
hydrocarbons. Additionally, mixed systems that include either a 1:1
or a 3:1 ratio of .alpha.-terpineol to toluene still resulted in
the recovery of about 77% and 92% of the total recoverable
hydrocarbons. This was an unexpected result.
TABLE-US-00008 TABLE 8 Extractable Ratio of Amount of Percent
Exposure Chemical Tar Sands HC Wt. of tar sands HC HC Temp, Time,
comp. wt., g wt., g solvent to solvent extracted, g extracted
.degree. C. minutes 60/30/10 60 2.0 60.0 1:1 7.1 91 96 30 terpineol
40/30/20 60 7.8 60.0 1:1 4.7 60 96 30 terpineol 70/20/10 60 7.8
60.0 1:1 7.9 101 96 30 terpineol 100/0/0 60 7.8 60.0 1:1 10.0 128
96 30 terpineol 100/0/0 60 7.8 120.0 1:2 8.7 111 96 30 terpineol
100/0/0 60 7.8 31.0 2:1 9.6 123 96 30 terpineol 50% .alpha.- 15 2.0
15.0 1:1 8.1 103 65 30 terpineol/ 50% ethanol 80% .alpha.- 15 2.0
15.0 1:1 1.2 62 15 15 terpineol/ 20% ethanol 75% .alpha.- 30 3.9
25.0 .sup. 1:0.8 1.8 92 15 15 terpineol/ 25% toluene 50% .alpha.-
30 3.9 26.0 .sup. 1:0.9 3.0 77 96 30 terpineol/ 50% toluene 50%
.alpha.- 30 3.9 26.0 .sup. 1:0.9 2.4 61 96 30 terpineol/ 50%
xylenes
Example 23
[0170] Approximately 30 g tar sands samples were sprayed with each
of the following liquids: d-limonene, a blend of turpentine
liquids, and water as a control. Temperature was maintained at
about 18.degree. C. The percent of bitumen recovered was measured
after a contact time of about 5, 10, 15, 20, 25, and 30 seconds.
The blend of turpentine liquids was a more effective extractor than
d-limonene, whereas water was ineffective (see FIG. 5).
Example 24
[0171] Approximately 15 g tar sands samples were sprayed with
d-limonene or a blend of turpentine liquids and left in contact
with the liquid for 97 seconds. The ratio of liquid to tar sands
ranged from approximately 1:1 to approximately 6:1. From 54%
recovery at 1:1 to 84% recovery at 6:1 ratios, the blend of
turpentine liquids extracted more bitumen than the limonene across
the range of mixing ratios (see FIG. 6).
Example 25
[0172] The effectiveness of a number of turpentine liquid species
and combinations for extracting hydrocarbon was measured relative
to the ability of each liquid to recover bitumen from a tar sands
sample. In each test, an approximately 15 g tar sands sample was
treated at about 18.degree. C. with one of the following turpentine
liquids: .alpha.-terpineol, .beta.-terpineol, .beta.-pinene,
.alpha.-pinene p-cymene, d-limonene, and a blend of turpentine
liquids. The percent of bitumen recovered was measured after
contact times of about 5 (FIG. 7) and about 15 (FIG. 8) minutes.
The data show that all of the liquids extracted a substantial
amount of the bitumen from the tar sands. The blend of turpentine
liquids was the most effective extractor across the range of liquid
to material ratios, recovering nearly all of the bitumen content
within about 5 minutes of contact (see FIG. 7).
Example 26
[0173] The amount of SAE 40 (a medium-weight crude oil) that could
be extracted by a blend of turpentine liquids was compared against
n-butanol, cyclohexanol, and 1-heptanol. At 35.degree. C., it was
found that the amount of SAE 40 extracted into 100 ml of a blend of
turpentine liquids consisting of about 50% .alpha.-terpineol, about
35% .beta.-terpineol, about 10% .beta.-pinene, and about 5%
p-cymene was approximately 8.14-, 6.67-, and 7.46-fold more than
the amount of SAE 40 that was extracted into 100 ml n-butanol, 100
ml cyclohexanol, and 100 ml 1-heptanol, respectively. Each of the
alkaline solutions contained 150 ml of 97% sodium metasilicate.
Example 27
[0174] Approximately 15 g and 30 g samples of paraffin wax, and
approximately 100 g samples of asphaltines were extracted into 100%
.alpha.-terpineol and 100% of a blend of turpentine liquids at
about 60.degree. C. for about 15 minutes. Table 9 shows the
percentage of hydrocarbon solids that were extracted into the
turpentine liquids.
Comparative Example
[0175] In a comparative example, the use of a liquid consisting of
about 1/3 terpenoids (limonene, pinene), about 1/3 heavy petroleum
distillates, and about 1/3 light petroleum distillates to liquefy
paraffin waxes and asphaltenes was compared against
.alpha.-terpineol and the multi-component turpentine system using
the same method as described in Example 27. A comparison of the
percentage of paraffin wax and asphaltines extracted is shown in
Table 9.
TABLE-US-00009 TABLE 9 % extracted % extracted 15 g 30 g 100 g 100
g paraffin paraffin asphaltine asphaltine Solvent wax wax (1) (2)
1/3 .beta.-Pinene, 1/3 heavy 60 60 42 47 crude, 1/3 light crude
Alpha terpineol 100 100 100 100 Blend of turpentine liquids 93.3 90
100 100
Example 28
[0176] Table 10 shows the decrease in viscosity of oils of
different weights after contact with turpentine liquids.
Measurements were taken within 20 seconds at a temperature of about
21.degree. C. The largest percentage drop in viscosity is obtained
by contacting heavier oils with a blend of turpentine liquids.
TABLE-US-00010 TABLE 10 Type of Viscosity Reducing Liquid %
viscosity Oil (weight % ratio to oil) Viscosity decrease SAE 40
None 718-750 N/A SAE 40 .alpha.-terpineol (10%) 697-699 7% (mean)
SAE 40 .alpha.-terpineol (15%) 569-620 21% (mean) SAE 40 Blend of
turpentine liquids (10%) 297 60% SAE 40 Blend of turpentine liquids
(15%) 245 67% SAE 30 None 156 N/A SAE 30 Blend of turpentine
liquids (10%) 109 30% SAE 30 Blend of turpentine liquids (15%) 88
44% SAE 10 None 49 N/A SAE 10 Blend of turpentine liquids (10%) 35
29%
Example 29
[0177] Corrosion Test. API X-65 carbon steel coupons (METAL SAMPLES
COMPANY, Munford, Ala., USA) were exposed to ASTM substitute
seawater with 500 ppm Na.sub.2S, pH adjusted to about 4.8 using
acetic acid, under continuous flow for two weeks. A control sample
contained only a baseline solution of the seawater in the absence
of corrosion inhibitor. Samples I, II, and III contained about
0.0005%, 0.001%, and 0.0015% by volume of a blend of turpentine
liquids. The corrosion rates recorded directly coincide with the
amount of crevice attack observed on each test coupon. Sample III,
consisting of about 0.0015% by volume of a blend of turpentine
liquids produced the lowest average corrosion rate (see Table 11)
and no pitting corrosion.
TABLE-US-00011 TABLE 11 Initial weight Final weight Average of
coupon (g) of coupon (g) corrosion Inhibitor Test 1 Test 2 Test 1
Test 2 rate (mpy) Baseline 16.1143 16.3113 16.1066 16.3037 0.36
solution only 5% Blend of 16.5291 16.7320 16.5247 16.7260 0.24
turpentine liquids 10% Blend of 17.0128 17.0229 17.0066 17.0172
0.28 turpentine liquids 15% Blend of 17.1076 16.4431 17.1056
16.4412 0.09 turpentine liquids
Example 30
[0178] The extracting ability of a surfactant free blend of
turpentine liquids was compared to d-limonene containing 0, 3, 9,
and 12% surfactant (Surfonic N-95 from Huntsman). The surfactant
free blend of turpentine liquids and d-limonene with surfactant
were contacted with 30 g of Super Pave Asphalt (weight of
aggregate: 92.9%, weight of asphalt: 6.6%, weight of polymer: 0.5%)
for two minutes, at a 1:1 ratio of liquid to asphalt at 45.degree.
C. The amount of asphalt recovery for the surfactant free blend of
turpentine liquids was 8.3%, while the d-limonene recovered only
4%, 6.3%, 5.3%, and 5.7% asphalt at 0, 3, 9, and 12% surfactant,
respectively. The surfactant-free blend of turpentine liquids
extracted more hydrocarbon-containing organic matter from asphalt
than d-limonene with or without surfactant.
[0179] The results for the extraction of hydrocarbon-containing
organic matter from hydrocarbon-containing material described in
the specification, and especially in the Examples above, were
unexpected.
[0180] As measured herein, the recovery, i.e., yield, in certain
samples exceeds 100% because certain hydrocarbon-containing
materials, e.g. tar sands, comprise heterogeneous and impure
mixtures of exceedingly viscous liquid and relatively coarse solid
particles, irregular in shape and varying in size. Thus, recovery
measurements based on the average value of hydrocarbon matter in
the hydrocarbon-containing materials at times exceed 100% due to
these naturally variable factors. Further, some experimental errors
are inherent to any experiment.
[0181] As used herein, the terms about and approximately should be
interpreted to include any values which are within 5% of the
recited value. Furthermore, recitation of the term about and
approximately with respect to a range of values should be
interpreted to include both the upper and lower end of the recited
range. As used herein, the terms first, second, third and the like
should be interpreted to uniquely identify elements and do not
imply or restrict to any particular sequencing of elements or
steps.
[0182] While the invention has been shown or described in only some
of its embodiments, it should be apparent to those skilled in the
art that it is not so limited, but is susceptible to various
changes without departing from the scope of the invention.
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